Low molecular weight copolymer of ethylene and vinyl aromatic monomer and uses thereof

ABSTRACT

An article of manufacture comprises a copolymer of ethylene and vinyl aromatic monomer having a molecular weight of less than 15,000. Preferably, the copolymer is characterized by a backbone having a first and second terminal end group, the first terminal end group is a methyl group, the second terminal end group is a vinyl group, wherein the ratio of the terminal methyl group to the terminal vinyl group is 0.8:1 to 1:0.8. The article of manufacture includes, but is not limited to, waxes, lubricants, additives, etc. The waxes may be used to formulate paints and coatings, printing inks, carbon paper, photo toners, building and construction materials, mold release agents, hot melt adhesives, candles. The waxes may also be used in wood processing, metal working, powder metallurgy and sintering, wax modeling, sizing, crop protection, and so on.

The invention relates to an article of manufacture comprising acopolymer of ethylene and vinyl aromatic monomer and variousapplications thereof.

Hydrocarbon waxes are widely used in a variety of applications such asin printing inks, processing aids, mould release agents, candles,polishes and particularly in coatings and adhesives. In particular,highly crystalline waxes are attracting increasing interest for admixingto produce abrasion-resistant printing inks, for paint flatting and forthe preparation of emulsifiable waxes for cleaning materials. Animportant application is in hot melt systems, particularly hot meltcoatings and hot melt adhesives. In general, paraffin waxes ormicrocrystalline waxes are used in such hot melt applications, butparaffin waxes and soft microcrystalline waxes both have relatively lowmelting points. Hard microcrystalline waxes have higher melting pointsbut are relatively expensive and have high viscosity. In some systemsthey also give rise to incompatibility problems.

Various synthetic techniques are used for preparing waxes. Thewell-known Fischer-Tropsch process produces waxy products, but thesematerials tend to have a higher molecular weight “tail” than paraffinwaxes which affects their properties. Waxes are also prepared bydegradation of higher molecular weight polyethylenes to obtain waxeswith the desired molecular weight. A further possibility is to preparewaxes directly by polymerization of ethylene or propylene. Atacticpolypropylene waxes tend to be sticky which results in handlingdifficulties, and in some systems these waxes are incompatible.Polyethylene waxes have in the past tended to be of higher molecularweight and thus higher viscosity than is required for many applications.

As generally known to those of skill in the art of olefinpolymerization, styrene is generally a relatively more difficultcomonomer to incorporate into an ethylene-α-olefin copolymer duringcopolymerization as compared with 1-hexene or 1-octene. See, forexample, Carlini et al., Polymer 42 (2001) 5069-5078 (“Thecopolymerization of styrene with α-olefins by conventional Ziegler-Nattacatalysts has been reported to occur with severe limitations.”).Moreover, most known ethylene styrene copolymers are directed towardpolymers where the styrene is present in a chain terminating position(see, for example, U.S. Pat. Nos. 3,390,141 and 5,180,872 and Pellecchiaet al., Macromolecules, 2000, 33, 2807-2814 and EP 0 526 943).Consequently, there remains a need to explore synthetic methods formaking a lower molecular weight ethylene styrene copolymer and toidentify various applications for such a copolymer.

The above need is met by one or more of the following aspects of theinvention. In one aspect, the invention relates to an article ofmanufacture comprising a copolymer of ethylene and vinyl aromaticmonomer having a molecular weight of less than 15,000. In someembodiments, the copolymer is characterized by a backbone having a firstand second terminal end group, the first terminal end group is a methylgroup, the second terminal end group is a vinyl group, wherein the ratioof the terminal methyl group to the terminal vinyl group is 0.8:1 to1:0.8. Optionally, the backbone of the copolymer is substantially freeof a vinylidene group. The article of manufacture includes, but is notlimited to, waxes, lubricants, additives, etc. The waxes may be used toformulate paints and coatings, printing inks, carbon paper, phototoners, building and construction materials, mold release agents, hotmelt adhesives, candles. The waxes may also be used in wood processing,metal working, powder metallurgy and sintering, wax modeling, sizing,crop protection, and so on. In some embodiments, the copolymer includesa functional group, such as a halogen, hydroxyl, anhydride, amine,amide, carboxylic acid, ester, ether, or nitrile group.

In another aspect, the invention relates to a method of functionalizinga polymer. The method comprises (a) obtaining a copolymer of ethyleneand vinyl aromatic monomer having a molecular weight of less than15,000, the copolymer being characterized by a backbone having a firstand second terminal end group, the first terminal end group being amethyl group, the second terminal end group being a vinyl group, whereinthe ratio of the terminal methyl group to the terminal vinyl group is0.8:1 to 1:0.8; and (b) effectuating functionalization of the vinylgroup to make a functionalized copolymer. The functionalizationincludes, but is not limited to, chlorination, epoxidation, oxidation,carboxylation, sulfonation and so on.

Additional aspects of the invention and the advantages of the inventionare apparent with the following description.

Embodiments of the invention provide a method of making a low molecularweight copolymer of ethylene vinyl aromatic monomer (“EVAM copolymer”)and applications thereof. Examples of suitable applications of the lowmolecular EVAM copolymer include, but are not limited to, waxes,lubricants, additives, etc. The waxes may be used to formulate paintsand coatings, printing inks, carbon paper, photo toners, building andconstruction materials, mold release agents, hot melt adhesives,candles. The waxes may also be used in wood processing, metal working,powder metallurgy and sintering, wax modeling, sizing, crop protection,and so on.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or“approximately” is used in connection therewith. They may vary by up to1 percent, 2 percent, 5 percent, or sometimes 10 to 20 percent. Whenevera numerical range with a lower limit, R_(L), and an upper limit R_(U),is disclosed, any number R falling within the range is specificallydisclosed. In particular, the following numbers R within the range arespecifically disclosed: R=R_(L)+k*(R_(U)−R_(L)), wherein k is a variableranging from 1 percent to 100 percent with a 1 percent increment, thatis k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . ,50 percent, 51 percent, 52 percent, . . . , 95 percent, 96 percent, 97percent, 98 percent, 99 percent, or 100 percent. Moreover, any numericalrange defined by two numbers, R, as defined in the above is alsospecifically disclosed.

The term “polymer” as used herein refers to a macromolecular compoundprepared by polymerizing monomers of the same or a different type. Apolymer refers to homopolymers, copolymers, terpolymers, interpolymers,and so on. The term “interpolymer” used herein refers to polymersprepared by the polymerization of at least two types of monomers orcomonomers. It includes, but is not limited to, copolymers (whichusually refers to polymers prepared from two different monomers orcomonomers), terpolymers (which usually refers to polymers prepared fromthree different types of monomers or comonomers), and tetrapolymers(which usually refers to polymers prepared from four different types ofmonomers or comonomers), and the like. The term “monomer” or “comonomer”refers to any compound with a polymerizable moiety which is added to areactor in order to produce a polymer.

The term “low molecular weight” refers to a weight average molecularweight of less than 30,000, preferably less than 15,000, 12,000, or10,000. However, the weight average molecular weight should be greaterthan about 300, preferably greater than 400. In some embodiments, ultralow molecular weight polymers are prepared. The term “ultra lowmolecular weight” refers to a weight average molecular weight of lessthan about 3,000. To be considered as a copolymer or interpolymer, itshould include at least two repeating units, preferably three, four,five, six, seven, or more. In some embodiments, the copolymer orinterpolymer includes at least ten repeating units. The molecular weightdistribution (MWD), which is the ratio of weight average molecularweight, M_(w), over number average molecular weight, M_(n), generally isbetween 1.1 and 6, preferably between 1.1 to 4, between 1.1 to 3, orbetween 1.1 to 2.5. In some embodiments, the MWD is less than about 2.In addition, the polymers disclosed herein generally possess anintrinsic viscosity (as measured in tetralin at 135° C.) of between0.025 and 0.9 dl/g, preferably of between 0.05 and 0.5 dl/g, mostpreferably of between 0.075 and 0.4 dl/g.

The low molecular weight copolymers or interpolymers may have variouscharacteristics which are described below.

As used herein, the phrase “characterized by the formula” is notintended to be limiting and is used in the same way that “comprising” iscommonly used. The term “independently selected” is used herein toindicate that the R groups, for example, R¹, R², R³, R⁴, and R⁵ can beidentical or different (for example R¹, R², R³, R⁴, and R⁵ may all besubstituted alkyls or R¹ and R² may be a substituted alkyl and R³ may bean aryl, etc.). Use of the singular includes use of the plural and viceversa (for example, a hexane solvent, includes hexanes). A named R groupwill generally have the structure that is recognized in the art ascorresponding to R groups having that name. The terms “compound” and“complex” are generally used interchangeably in this specification, butthose of skill in the art may recognize certain compounds as complexesand vice versa. For the purposes of illustration, representative certaingroups are defined herein. These definitions are intended to supplementand illustrate, not preclude, the definitions known to those of skill inthe art. Also as used herein “styrene” is intended to includesubstituted versions of styrene, such as para-t-butyl-styrene.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to30 carbon atoms, preferably 1 to 24 carbon atoms, most preferably 1 to12 carbon atoms, including branched or unbranched, saturated orunsaturated species, such as alkyl groups, alkenyl groups, aryl groups,and the like. “Substituted hydrocarbyl” refers to hydrocarbylsubstituted with one or more substituent groups, and the terms“heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer tohydrocarbyl in which at least one carbon atom is replaced with aheteroatom.

The term “alkyl” is used herein to refer to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Suitable alkylradicals include, for example, methyl, ethyl, n-propyl, i-propyl,2-propenyl (or allyl), vinyl, n-butyl, t-butyl, i-butyl (or2-methylpropyl), etc. In particular embodiments, alkyls have between 1and 200 carbon atoms, between 1 and 50 carbon atoms or between 1 and 20carbon atoms.

“Substituted alkyl” refers to an alkyl as just described in which one ormore hydrogen atom bound to any carbon of the alkyl is replaced byanother group such as a halogen, aryl, substituted aryl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,halogen, alkylhalos (for example, CF₃), hydroxy, amino, phosphido,alkoxy, amino, thio, nitro, and combinations thereof. Suitablesubstituted alkyls include, for example, benzyl, trifluoromethyl and thelike.

The term “heteroalkyl” refers to an alkyl as described above in whichone or more hydrogen atoms to any carbon of the alkyl is replaced by aheteroatom selected from the group consisting of N, O, P, B, S, Si, Sb,Al, Sn, As, Se and Ge. This same list of heteroatoms is usefulthroughout this specification. The bond between the carbon atom and theheteroatom may be saturated or unsaturated. Thus, an alkyl substitutedwith a heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, or seleno is within the scope of the term heteroalkyl. Suitableheteroalkyls include cyano, benzoyl, 2-pyridyl, 2-furyl and the like.

The term “cycloalkyl” is used herein to refer to a saturated orunsaturated cyclic non-aromatic hydrocarbon radical having a single ringor multiple condensed rings. Suitable cycloalkyl radicals include, forexample, cyclopentyl, cyclohexyl, cyclooctenyl, bicyclooctyl, etc. Inparticular embodiments, cycloalkyls have between 3 and 200 carbon atoms,between 3 and 50 carbon atoms or between 3 and 20 carbon atoms.

“Substituted cycloalkyl” refers to cycloalkyl as just describedincluding in which one or more hydrogen atom to any carbon of thecycloalkyl is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substituted cycloalkylradicals include, for example, 4-dimethylaminocyclohexyl,4,5-dibromocyclohept-4-enyl, and the like.

The term “heterocycloalkyl” is used herein to refer to a cycloalkylradical as described, but in which one or more or all carbon atoms ofthe saturated or unsaturated cyclic radical are replaced by a heteroatomsuch as nitrogen, phosphorous, oxygen, sulfur, silicon, germanium,selenium, or boron. Suitable heterocycloalkyls include, for example,piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl,piperidinyl, pyrrolidinyl, oxazolinyl and the like.

“Substituted heterocycloalkyl” refers to heterocycloalkyl as justdescribed including in which one or more hydrogen atom to any atom ofthe heterocycloalkyl is replaced by another group such as a halogen,alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl,thio, seleno and combinations thereof. Suitable substitutedheterocycloalkyl radicals include, for example, N-methylpiperazinyl,3-dimethylaminomorpholinyl and the like.

The term “aryl” is used herein to refer to an aromatic substituent,which may be a single aromatic ring or multiple aromatic rings, whichare fused together, linked covalently, or linked to a common group suchas a methylene or ethylene moiety. The aromatic ring(s) may includephenyl, naphthyl, anthracenyl, and biphenyl, among others. In particularembodiments, aryls have between 1 and 200 carbon atoms, between 1 and 50carbon atoms or between 1 and 20 carbon atoms.

“Substituted aryl” refers to aryl as just described in which one or morehydrogen atom bound to any carbon is replaced by one or more functionalgroups such as alkyl, substituted alkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen,alkylhalos (for example, CF₃), hydroxy, amino, phosphido, alkoxy, amino,thio, nitro, and both saturated and unsaturated cyclic hydrocarbonswhich are fused to the aromatic ring(s), linked covalently or linked toa common group such as a methylene or ethylene moiety. The commonlinking group may also be a carbonyl as in benzophenone or oxygen as indiphenylether or nitrogen in diphenylamine.

The term “heteroaryl” as used herein refers to aromatic rings in whichone or more carbon atoms of the aromatic ring(s) are replaced by aheteroatom(s) such as nitrogen, oxygen, boron, selenium, phosphorus,silicon or sulfur. Heteroaryl refers to structures that may be a singlearomatic ring, multiple aromatic ring(s), or one or more aromatic ringscoupled to one or more non-aromatic ring(s). In structures havingmultiple rings, the rings can be fused together, linked covalently, orlinked to a common group such as a methylene or ethylene moiety. Thecommon linking group may also be a carbonyl as in phenyl pyridyl ketone.As used herein, rings such as thiophene, pyridine, isoxazole, pyrazole,pyrrole, furan, etc. or benzo-fused analogues of these rings are definedby the term “heteroaryl.”

“Substituted heteroaryl” refers to heteroaryl as just describedincluding in which one or more hydrogen atoms bound to any atom of theheteroaryl moiety is replaced by another group such as a halogen, alkyl,substituted alkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio,seleno and combinations thereof. Suitable substituted heteroarylradicals include, for example, 4-N,N-dimethylaminopyridine.

The term “alkoxy” is used herein to refer to the —OZ¹ radical, where Z¹is selected from the group consisting of alkyl, substituted alkyl,cycloalkyl, substituted cycloalkyl, heterocylcoalkyl, substitutedheterocycloalkyl, silyl groups and combinations thereof as describedherein. Suitable alkoxy radicals include, for example, methoxy, ethoxy,benzyloxy, t-butoxy, etc. A related term is “aryloxy” where Z¹ isselected from the group consisting of aryl, substituted aryl,heteroaryl, substituted heteroaryl, and combinations thereof. Examplesof suitable aryloxy radicals include phenoxy, substituted phenoxy,2-pyridinoxy, 8-quinalinoxy and the like.

As used herein the term “silyl” refers to the —SiZ¹Z²Z³ radical, whereeach of Z¹, Z², and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,substituted heteroaryl, alkoxy, aryloxy, amino, silyl and combinationsthereof.

As used herein the term “boryl” refers to the —BZ¹Z² group, where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, heterocycloalkyl,heterocyclic, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, amino, silyl and combinations thereof.

As used herein, the term “phosphino” refers to the group —PZ¹Z², whereeach of Z¹ and Z² is independently selected from the group consisting ofhydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

As used herein, the term “phosphine” refers to the group: PZ¹Z²Z³, whereeach of Z¹, Z³ and Z² is independently selected from the groupconsisting of hydrogen, substituted or unsubstituted alkyl, cycloalkyl,heterocycloalkyl, heterocyclic, aryl, substituted aryl, heteroaryl,silyl, alkoxy, aryloxy, amino and combinations thereof.

The term “amino” is used herein to refer to the group —NZ¹Z², where eachof Z¹ and Z² is independently selected from the group consisting ofhydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl,heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl andcombinations thereof.

The term “amine” is used herein to refer to the group: NZ¹Z²Z³, whereeach of Z¹, Z² and Z³ is independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl (including pyridines), substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “thio” is used herein to refer to the group —SZ¹, where Z¹ isselected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “seleno” is used herein to refer to the group —SeZ¹, where Z¹is selected from the group consisting of hydrogen, alkyl, substitutedalkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, silyl and combinations thereof.

The term “halo” refers to Cl, F, Br or I bonded to a carbon and “halide”refers to Cl, F, Br or I bonded to a metal.

The term “saturated” refers to lack of double and triple bonds betweenatoms of a radical group such as ethyl, cyclohexyl, pyrrolidinyl, andthe like.

The term “unsaturated” refers to the presence one or more double andtriple bonds between atoms of a radical group such as vinyl, acetylide,oxazolinyl, cyclohexenyl, acetyl and the like.

The term “substantially random” (in the substantially randominterpolymer comprising polymeric units derived from one or moreα-olefin monomers with one or more vinyl aromatic monomers and/oraliphatic or cycloaliphatic vinyl or vinylidene monomers) as used hereinmeans that the distribution of the monomers of said interpolymer can bedescribed by the Bernoulli statistical model or by a first or secondorder Markovian statistical model, as described by J. C. Randall inPOLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method, Academic Press NewYork, 1977, pp. 71-78. Preferably, substantially random interpolymers donot contain more than 15 percent of the total amount of vinyl aromaticmonomer in blocks of vinyl aromatic monomer of more than 3 units. Morepreferably, the interpolymer is not characterized by a high degree ofeither isotacticity or syndiotacticity. This means that in the carbon¹³NMR spectrum of the substantially random interpolymer the peak areascorresponding to the main chain methylene and methine carbonsrepresenting either meso diad sequences or racemic diad sequences shouldnot exceed 75 percent of the total peak area of the main chain methyleneand methine carbons.

Substantially Random Interpolymers

In some embodiments, the low molecular weight copolymers orinterpolymers are substantially random olefin interpolymer whichcomprises:

-   (1) first polymeric units derived from:-   (i) at least one vinyl aromatic monomer, or-   (ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene    monomer, or-   (iii) a combination of at least one aromatic vinyl monomer and at    least one aliphatic or cycloaliphatic vinyl or vinylidene monomer,    and-   (2) second polymeric units derived from at least one C₂₋₂₀ α-olefin;    and optionally-   (3) third polymeric units derived from one or more ethylenically    unsaturated polymerizable monomers other than those of (1) and (2).

The first polymeric units may be present in the interpolymer in anyamount, such as from 0.5 mol. percent to 99.5 mol. percent, from 5 mol.percent to 90 mol. percent; from 10 mol. percent to 75 mol. percent;from 1 mol. percent to 50 mol. percent; from 10 mol. percent to 45 mol.percent; or from 5 mol. percent to 35 mol. percent. Preferably, thefirst polymeric units are present in an amount of 50 mol. percent orless. Similarly, the second polymeric unit may be present in theinterpolymer in the above ranges. In some embodiments, the secondpolymeric units are present in an amount of 50 mol. percent or higher.In other embodiments, the second polymeric units are present in anamount higher than the first polymeric units. The third polymeric unitsare optional and may be present up to 50 mol. percent, preferably up to40 mol. percent, up to 30 mol. percent, up to 20 mol. percent, up to 10mol. percent, or up to 5 mol. percent.

Suitable α-olefins include for example, α-olefins containing from 2 to20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms.Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethylene in combination withone or more of propylene, butene-1, 4-methyl-1-pentene, hexene-1 oroctene-1. These α-olefins do not contain an aromatic moiety.

Other optional polymerizable ethylenically unsaturated monomer(s)include strained ring olefins such as norbornene and C₁₋₁₀ alkyl orC₆₋₁₀ aryl substituted norbornenes, with an exemplary interpolymer beingethylene/styrene/norbornene.

Suitable vinyl aromatic monomers which can be employed to prepare theinterpolymers include, for example, those represented by the followingformula:

wherein R¹ is selected from the group of radicals consisting of hydrogenand alkyl radicals containing from 1 to 4 carbon atoms, preferablyhydrogen or methyl; each R² is independently selected from the group ofradicals consisting of hydrogen and alkyl radicals containing from 1 to4 carbon atoms, preferably hydrogen or methyl; the two R² groups can bethe same or different groups. Ar is a phenyl group or a phenyl groupsubstituted with from 1 to 5 substituents selected from the groupconsisting of halo, C₁₋₄-alkyl, and C₁₋₄-haloalkyl; and n has a valuefrom zero to 4, preferably from zero to 2, most preferably zero.Exemplary monovinyl aromatic monomers include styrene, vinyl toluene,α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomersof these compounds, and the like. Particularly suitable monomers includestyrene and lower alkyl- or halogen-substituted derivatives thereof.Preferred monomers include styrene, α-methyl styrene, the loweralkyl-(C₁-C₄) or phenyl-ring substituted derivatives of styrene, such asortho-, meta-, and para-methylstyrene, the ring halogenated styrenes,para-vinyl toluene or mixtures thereof, and the like. A more preferredaromatic monovinyl monomer is styrene.

By the term “aliphatic or cycloaliphatic vinyl or vinylidene compounds”,it is meant addition polymerizable vinyl or vinylidene monomerscorresponding to the formula:

wherein A¹ is a sterically bulky, aliphatic or cycloaliphaticsubstituent of up to 20 carbons, R¹ is selected from the group ofradicals consisting of hydrogen and alkyl radicals containing from 1 to4 carbon atoms, preferably hydrogen or methyl; alternatively R¹ and A¹together may form a ring system. Each R² is independently selected fromthe group of radicals consisting of hydrogen and alkyl radicalscontaining from 1 to 4 carbon atoms, preferably hydrogen or methyl; thetwo R² groups can be the same or different groups. Preferred aliphaticor cycloaliphatic vinyl or vinylidene compounds are monomers in whichone of the carbon atoms bearing ethylenic unsaturation is tertiary orquaternary substituted. Examples of such substituents include cyclicaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ringalkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl,and the like. Most preferred aliphatic or cycloaliphatic vinyl orvinylidene compounds are the various isomeric vinyl-ring substitutedderivatives of cyclohexene and substituted cyclohexenes, and5-ethylidene-2-norbornene. Especially suitable are 1-, 3-, and4-vinylcyclohexene.

The substantially random interpolymers can be prepared as described inEP-A-0,416,815 by James C. Stevens et al. and U.S. Pat. No. 5,703,187 byFrancis J. Timmers. Such a method of preparation of the substantiallyrandom interpolymers includes polymerizing a mixture of polymerizablemonomers in the presence of one or more metallocene or constrainedgeometry catalysts in combination with various cocatalysts. Preferredoperating conditions for such polymerization reactions are pressuresfrom atmospheric up to 3000 atmospheres and temperatures from −30° C. to200° C. Polymerizations and unreacted monomer removal at temperaturesabove the autopolymerization temperature of the respective monomers mayresult in formation of some amounts of homopolymer polymerizationproducts resulting from free radical polymerization. Additional methodsare disclosed in U.S. Pat. No. 6,344,515.

Examples of suitable catalysts and methods for preparing thesubstantially random interpolymers are disclosed in EP-A-514,828; aswell as U.S. Pat. Nos. 5,055,438; 5,057,475; 5,096,867; 5,064,802;5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696;5,399,635; 5,470,993; 5,703,187; and 5,721,185.

The substantially random α-olefin/vinyl aromatic interpolymers can alsobe prepared by the methods described in JP 07/278,230 employingcompounds shown by the general formula

where Cp¹ and Cp² are cyclopentadienyl groups, indenyl groups, fluorenylgroups, or substituents of these, independently of each other; R¹ and R²are hydrogen atoms, halogen atoms, hydrocarbon groups with carbonnumbers of 1-12, alkoxyl groups, or aryloxyl groups, independently ofeach other; M is a group IV metal, preferably Zr or Hf, most preferablyZr; and R³ is an alkylene group or silanediyl group used to cross-linkCp¹ and Cp²).

The substantially random α-olefin/vinyl aromatic interpolymers can alsobe prepared by the methods described by John G. Bradfute et al. (W. RGrace & Co.) in WO 95/32095; by R. B. Pannell (Exxon Chemical Patents,Inc.) in WO 94/00500; and in Plastics Technology, p. 25 (September1992).

Also suitable are the substantially random interpolymers which compriseat least one α-olefin/vinyl aromatic/vinyl aromatic/α-olefin tetraddisclosed in WO 98/09999 by Francis J. Timmers, et al. Theseinterpolymers contain additional signals in their carbon-13 NMR spectrawith intensities greater than three times the peak to peak noise. Thesesignals appear in the chemical shift range 43.70-44.25 ppm and 38.0-38.5ppm. Specifically, major peaks are observed at 44.1, 43.9, and 38.2 ppm.A proton test NMR experiment indicates that the signals in the chemicalshift region 43.70-44.25 ppm are methine carbons and the signals in theregion 38.0-38.5 ppm are methylene carbons.

It is believed that these new signals are due to sequences involving twohead-to-tail vinyl aromatic monomer insertions preceded and followed byat least one α-olefin insertion, for example anethylene/styrene/styrene/ethylene tetrad wherein the styrene monomerinsertions of said tetrads occur exclusively in a 1,2 (head to tail)manner. It is understood by one skilled in the art that for such tetradsinvolving a vinyl aromatic monomer other than styrene and an α-olefinother than ethylene that the ethylene/vinyl aromatic monomer/vinylaromatic monomer/ethylene tetrad will give rise to similar carbon ¹³NMRpeaks but with slightly different chemical shifts.

These interpolymers can be prepared by conducting the polymerization attemperatures of from −30° C. to 250° C. in the presence of suchcatalysts as those represented by the formula

wherein: each Cp is independently, each occurrence, a substitutedcyclopentadienyl group π-bound to M; E is C or Si; M is a group IVmetal, preferably Zr or Hf, most preferably Zr; each R is independently,each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl,containing up to 30 preferably from 1 to 20 more preferably from 1 to 10carbon or silicon atoms; each R′ is independently, each occurrence, H,halo, hydrocarbyl, hyrocarbyloxy, silahydrocarbyl, hydrocarbylsilylcontaining up to 30 preferably from 1 to 20 more preferably from 1 to 10carbon or silicon atoms or two R′ groups together can be a C₁₋₁₀hydrocarbyl substituted 1,3-butadiene; m is 1 or 2; and optionally, butpreferably in the presence of an activating cocatalyst. Particularly,suitable substituted cyclopentadienyl groups include those illustratedby the formula:

wherein each R is independently, each occurrence, H, hydrocarbyl,silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferablyfrom 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or twoR groups together form a divalent derivative of such group. Preferably,R independently each occurrence is (including where appropriate allisomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl,phenyl or silyl or (where appropriate) two such R groups are linkedtogether forming a fused ring system such as indenyl, fluorenyl,tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.

Particularly preferred catalysts include, for example,racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconiumdichloride,racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconium1,4-diphenyl-1,3-butadiene,racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconiumdi-C1-4 alkyl,racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl)) zirconiumdi-C1-4 alkoxide, or any combination thereof and the like.

It is also possible to use the following titanium-based constrainedgeometry catalysts,[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydro-s-indacen-1-yl]silanaminato(2-)-N]titaniumdimethyl; (1-indenyl)(tert-butylamido)dimethyl-silane titanium dimethyl;((3-tert-butyl)(1,2,3,4,5-η)-1-indenyl)(tert-butylamido)dimethylsilanetitanium dimethyl; and((3-iso-propyl)(1,2,3,4,5-η)-1-indenyl)(tert-butyl amido)dimethyl silanetitanium dimethyl,[1-[(1,2,3,3a,11b-η)-1H-cyclopenta[1]phenanthren-2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-κN]dimethyl-titanium,[1-[(1,2,3,3a,12b-η)-2,8-dihydrodibenz[e,h]azulen-2-yl]-N-(1,1-dimethylethyl)-1,1-dimethylsilanaminato(2-)-κN]dimethyltitanium, or any combination thereof and the like.

Examples of additional suitable catalysts include, but are not limitedto, dimethylmethylene bis(4,5-benz-1-indenyl)zirconium dichloride(another name: dimethylmethylenebis(benz-e-indenyl)zirconiumdichloride), di-n-propylmethlenebis(4,5-benz-1-indenyl)zirconiumdichloride, di-i-propylmethylenebis(4,5-benz-1-indenyl)zirconiumdichloride, cyclohexylidenebis(4,5-benz-1-indenyl)zirconium dichloride,cyclopentylidenebis(4,5-benz-1-indenyl)zirconium dichloride,diphenylmethylenebis(4,5-benz-1-indenyl)zirconium dichloride,dimethylmethylene(cyclopentadienyl)(4,5-benz-1-indenyl)zirconiumdichloride, dimethylmethylene(1-indenyl)(4,5-benz-1-indenyl)zirconiumdichloride, dimethyl methylene(1-fluorenyl)(4,5-benz-1-indenyl)zirconiumdichloride,dimethylmethylene(4-phenyl-1-indenyl)(4,5-benz-1-indenyl)zirconiumdichloride,dimethylmethylene(4-naphthyl-1-indenyl)(4,5-benz-1-indenyl)zirconiumdichloride, dimethylmethylenebis(5,6-benz-1-indenyl)zirconiumdichloride, dimethylmethylene(5,6-benz-1-indenyl)(1-indenyl)zirconiumdichloride, dimethylmethylenebis(4,7-benz-1-indenyl)zirconiumdichloride, dimethyl methylene(6,7-benz-1-indenyl)(1-indenyl)zirconiumdichloride, dimethylmethylene bis(4,5-naphtho-1-indenyl)zirconiumdichloride,dimethylmethylenebis(.alpha.-acetonaphtho-1-indenyl)zirconiumdichloride, dimethylmethylenebis(3-cyclopenta(c)phenanthryl)zirconiumdichloride,dimethylmethylene(3-cyclopenta(c)phenanthryl)(1-indenyl)zirconiumdichloride, dimethylmethylenebis(1-cyclopenta(1)phenanthryl)zirconiumdichloride, dimethylmethylene(1-cyclopenta(1)phenanthryl)(1-indenyl)zirconium dichloride,dimethylmethylenebis(4,5-benz-1-indenyl)zirconium bis(dimethylamide),and dimethylmethylene(1-indenyl)(4,5-benz-1-indenyl)zirconiumbis(dimethylamide).

Suitable catalysts also include, are not limited to,dimethylmethylenebis(3-cyclopenta[c]phenanthryl)zirconium dichloride,di-n-propylmethylenebis(3-cyclopenta[c]phenanthryl)zirconium dichloride,di-i-propylmethylenebis(3-cyclopenta[c]phenanthryl)zirconium dichloride,cyclohexylidenebis(3-cyclopenta[c]phenanthryl)zirconium dichloride,cyclopentylidenebis(3-cyclopenta[c]phenanthryl)zirconium dichloride,diphenylinethylenebis(3-cylcopenta[c]phenanthryl)zirconium dichloride,dimethylmethylene(4,5-benzo-1-indenyl)(3-cylcopenta[c]phenanthryl)zirconium dichloride,dimethylmethylene(5,6-benzo-1-indenyl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride,dimethylmethylene(6,7-benzo-1-indenyl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride, dimethylmethylene(cyclopentadienyl)(3-cyclopenta[c]phenanthryl)zirconium dichloride,dimethylmethylene (1-fluorenyl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride,dimethylmethylene(4-phenyl-1-indenyl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride,dimethylmethylene(4-naphthyl-1-indenyl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride,dimethylmethylene(3-cyclopenta[c]phenanthryl)(4,5-naphto-1-indenyl)zirconiumdichloride,dimethylmethylene(3-cyclopenta[c]phenanthryl(.alpha.-acenaphto-1-indenyl)zirconiumdichloride, dimethyl methylenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, di-n-propylmethylenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, di-i-propylmethylenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, cyclohexylidenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, cyclopentylidenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, diphenyl methylenebis(1-cyclopenta[1]phenanthryl)zirconiumdichloride, diphenylmethylene(4,5-benzo-1-indenyl)(1-cyclopenta[1]phenanthryl)zirconium dichloride,diphenylmethylene(5,6-benzo-1-indenyl)(1-cyclopenta[1]phenanthryl)zirconiumdichloride,diphenylmethylene(6,7-benzo-1-indenyl)(1-cyclopenta[1]phenanthryl)zirconiumdichloride, methylmethylene(cyclopentadienyl)(1-cyclopenta[1]iphenanthryl)zirconium dichloride,dimethylmethylene(1-fluorenyl)(1-cyclopenta[1]phenanthryl)zirconiumdichloride,dimethylmethylene(4-phenyl-1-indenyl)(1-cyclopenta[1]phenanthryl)zirconiumdichloride,dimethylmethylene(4-naphthyl-1-indenyl)(1-cyclopenta[1]phenanthryl)zirconiumdichloride, dimethylmethylene(1-cyclopenta[1]phenanthryl)(4,5-naphtho-1-indenyl)zirconium dichloride,dimethylmethylene(1-cyclopenta[1]phenanthryl)(.alpha.-acenaphtho-1-indenyl)zirconiumdichloride, dimethylmethylene(1-cyclopenta[1]phenanthryl)(3-cyclopenta[c]phenanthryl)zirconiumdichloride, and the like.

In the foregoing, zirconium complexes were exemplified, butcorresponding titanium complexes and hafnium complexes may also suitablybe used. Further, racemic-form or mixtures of racemic-form and meso-formmay also be employed. Preferably, racemic-form or pseudo racemic-formare employed. In such a case, D-isomers or L-isomers may be employed.

Further preparative methods for the interpolymers used in embodiments ofthe invention have been described in the literature. Longo and Grassi(Makromol. Chem., Volume 191, pages 2387 to 2396 [1990]) and D'Annielloet al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706[1995]) reported the use of a catalytic system based on methylalumoxane(MAO) and cyclopentadienyltitanium trichloride (CpTiCl₃) to prepare anethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem.Soc. Div. Polym. Chem.) Volume 35, pages 686, 687 [1994]) have reportedcopolymerization using a MgCl₂/TiCl₄/NdCl₃/Al(iBu)₃ catalyst to giverandom copolymers of styrene and propylene. Lu et al (Journal of AppliedPolymer Science, Volume 53, pages 1453 to 1460 [1994]) have describedthe copolymerization of ethylene and styrene using aTiCl₄/NdCl₃/MgCl₂/Al(Et)₃ catalyst. Sernetz and Mulhaupt, (Macromol.Chem. Phys., v. 197, pp. 1071-1083, 1997) have described the influenceof polymerization conditions on the copolymerization of styrene withethylene using Me₂Si(Me₄Cp)(N-tert-butyl)TiCl₂/methylaluminoxaneZiegler-Natta catalysts. Copolymers of ethylene and styrene produced bybridged metallocene catalysts have been described by Arai, Toshiaki andSuzuki (Polymer Preprints, Am. Chem. Soc. Div. Polym. Chem.) Volume 38,pages 349, 350 [1997]) and in U.S. Pat. No. 5,652,315, issued to MitsuiToatsu Chemicals, Inc. The manufacture of α-olefin/vinyl aromaticmonomer interpolymers such as propylene/styrene and butene/styrene aredescribed in U.S. Pat. No. 5,244,996, issued to Mitsui PetrochemicalIndustries Ltd or U.S. Pat. No. 5,652,315 also issued to MitsuiPetrochemical Industries Ltd or as disclosed in DE 197 11 339 A1 toDenki KAGAKU Kogyo KK. While preparing the substantially randominterpolymer, an amount of atactic vinyl aromatic homopolymer may beformed due to homopolymerization of the vinyl aromatic monomer atelevated temperatures. The presence of vinyl aromatic homopolymer is ingeneral not detrimental and can be tolerated. The vinyl aromatichomopolymer may be separated from the interpolymer, if desired, byextraction techniques such as selective precipitation from solution witha non solvent for either the interpolymer or the vinyl aromatichomopolymer. It is preferred that no more than 30 weight percent,preferably less than 20 weight percent based on the total weight of theinterpolymers of atactic vinyl aromatic homopolymer is present.

Interpolymers with Vinyl End Groups

In some embodiments, the copolymers or interpolymers are characterizedby one methyl end group attached to one end of the polymeric chain andone vinyl end group attached to the other end of the polymeric chain,where the ratio of methyl to vinyl is at least 0.5, preferably 0.8 to1.25 or 0.9 to 1.11. Some copolymers or interpolymers are substantiallyfree of a vinylidene end group or a vinylidene structure in thepolymeric chain. Such copolymers or interpolymers can be prepared by themethods disclosed in currently filed U.S. patent application entitled“Ethylene-Styrene Copolymers and Phenol-Triazole Type Complexes,Catalysts, and Processes for Polymerizing,” with the followinginventors: Oliver Brummer, Gary M. Diamond, Christopher Goh, Anne M.LaPointe, Margaret Leclere, James Longmire, and James A. W. Shoemaker,U.S. application Ser. No. 10/121,300, filed on Apr. 12, 2002.

In some embodiments, low molecular weight ethylene-styrene copolymersare prepared according to the methods disclosed in the above referencedcurrently filed patent application. The ethylene-styrene copolymers havea relatively low molecular weight (less than 10,000 and morespecifically less than 5,000, less than 3,000 or less than 1,000)combined with a relatively narrow molecular weight distribution (lessthan 2.5 and more specifically less than 2.0) and end-group, determinedby NMR end-group analysis that show a ratio of methyl to vinyl in therange of from 0.8:1 to 1:0.8 and more specifically 0.9:1 to 1:0.9. Themolecular weights may be weight averages or number averages. Theend-group analysis is performed using proton nuclear magnetic resonance(NMR) techniques, which are relatively well known to those of skill inthe art. The scientific error in this method is 10-20 percent, given theability to integrate the area under the peaks based on the relativelysmall peaks associated with the vinyl and methyl hydrogen atoms ascompared to the much larger peaks associated with the hydrogen atomsfrom the backbone of the polymer as well as given the close proximity ofthe shifts of the large methylene and small methyl peaks in the NMRspectrum. As those of skill in the art will appreciate, the peaks mightbe integrated more accurately with higher power NMR equipment. Endanalysis was performed in the manner discussed in the examples herein.The molecular weight and polydispersity are determined using sizeexclusion chromatography according to methods known to those of skill inthe art, such as relative to linear polystyrene standards. See U.S. Pat.Nos. 6,294,388, 6,260,407, 6,175,409, 6,296,771 and 6,265,226.

The copolymers also show that the styrene monomer(s) incorporated intothe chain do not lie just at one of the ends of the polymer, but arerandomly distributed along the polymer backbone. In this regard, thepolymers made in some embodiments of the invention can be characterizedby either of the general formulas I or II:

wherein h, i and j are each a number greater than or equal to 1.

Under the polymerization conditions chosen for some embodiments, thedegree of polymerization, which corresponds to the formula((h+i+1)*j)+2, in a bulk sample is between 5 and 100, based on protonNMR analysis, more specifically between 5 and 50 and even morespecifically between 5 and 25. In addition, the number of styrenemonomers (j) in a bulk sample is between 1 and 10, more specificallybetween 1 and 5 and even more specifically between 1 and 3. Inalternative embodiments, the number of styrene monomers (j) in a bulksample is between 2 and 10 and more specifically between 2 and 5.Testing to determine these numbers is typically by proton NMR, but othertechniques known to those of skill in the art may also be employed.

The low molecular weight ethylene-styrene copolymers made in someembodiments of the invention differ significantly from any previouslyreported ethylene-styrene copolymers or co-oligomers. The products haveon average one or more styrene units incorporated per chain, such thatthe incorporated styrene unit is essentially randomly distributed alongthe length of the chain, such that the typical chain has a methyl (—CH₃)group at one end and a vinyl (—CH═CH₂) group at the other end. Thus theproducts are essentially linear α-olefins with phenyl substituentsplaced essentially randomly along the length of the chain. Suitablemetal-ligand complexes, which are useful as catalysts for the productionof the styrene-ethylene copolymers discussed above, are those generallyhaving two non-leaving group (or ancillary) phenol-heterocycle orphenol-triazole ligands attached to the metal center. In other words,there is a 2:1 ligand to metal ratio intended (although such ratio maynot be exact). Such metal complexes may be characterized by thefollowing general formula:

wherein X¹ and X² are N, and X³, X⁴, and X⁵ are independently selectedfrom the group consisting of N and CR¹⁵, where R¹⁵ is selected from thegroup consisting of hydrogen, alkyl, substituted alkyl, cycloalkyl,substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl,aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy,aryloxy, halo, silyl, boryl, phosphino, amino, thio, seleno, andcombinations thereof, provided that at least one and not more than twoof X³, X⁴, and X⁵ are N; optionally, X³ and X⁴ may be joined to form afused ring system having up to 50 atoms, not counting hydrogen atoms.

In general, R¹, R², R³ and R⁴ are independently selected from hydrogen,alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl,heteroalkyl, substituted heteroalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, alkoxy, aryloxy, halo, silyl, boryl, phosphino, amino, thio,seleno, nitro, and combinations thereof, with the exception that R¹ maynot be hydrogen, and optionally two or more of R¹, R², R³ and R⁴ (forexample R¹ and R², or R² and R³, or R³ and R⁴) may be joined to form afused ring system having up to 50 atoms, not counting hydrogens. In theabove formula, however, R² and R⁴ are both hydrogen or are joined in afused ring system, as described;

-   M is zirconium, titanium or hafnium; and-   L¹ and L² are independently selected from the group consisting of    halide, alkyl, substituted alkyl, cycloalkyl, substituted    cycloalkyl, heteroalkyl, substituted heteroalkyl, heterocycloalkyl,    substituted heterocycloalkyl, aryl, substituted aryl, heteroaryl,    substituted heteroaryl, alkoxy, aryloxy, hydroxy, thio, boryl,    silyl, amino, hydrido, allyl, seleno, phosphino, carboxylates, and    combinations thereof.

It should be understood that the numbers for h, i and j (as describedabove) are dependant on the polymerization conditions chosen, includingthe amount of ethylene, amount of styrene, temperature, pressure,catalyst concentration and structure (including the activator(s) oractivating package). Thus, both the catalyst ligand structure and choiceof metal may influence the ethylene-styrene copolymerization catalystperformance and product properties. Under the specific polymerizationconditions set forth in the examples herein, some general trendsincluded: (i) an aryl (for example phenyl, naphthyl or anthracenyl)substituent at the ortho position of the phenol (R¹) generally resultsin higher styrene incorporation into the copolymer product compared to atert-butyl substituent at the ortho position, (ii) zirconiumcompositions and complexes have given higher activity, higher styreneincorporation, and lower molecular weight products than analogoushafnium compositions and complexes, (iii) halo, especially chloro,substitution on the aromatic ring results in increased activity comparedwith H at these positions, (iv) methoxy (—OMe) substitution at the paraposition of the phenol (R³) results in higher molecular weight productas compared to a tert-butyl substitution at this position, (v) an aryl(for example phenyl, naphthyl or anthracenyl) substituent at the orthoposition of the phenol (R¹) results in longer catalyst lifetime at hightemperature as compared to a tert-butyl substituent at the orthoposition, there are ligand effects, metal effects and activator effects.While these trends were found for the specific polymerization conditionsemployed herein, some or all of these trends might be modified underdifferent polymerization conditions.

Polymerization Systems

Polymerization can be carried out in the Ziegler-Natta or Kaminsky-Sinnmethodology, including temperatures of from −100° C. to 300° C. andpressures from atmospheric to 3000 atmospheres. Suspension, solution,slurry, gas phase or high-pressure polymerization processes may beemployed with the catalysts and compounds described herein. Suchprocesses can be run in a batch, semi-batch or continuous mode. Examplesof such processes are well known in the art. A support for the catalystmay be employed, which may be inorganic (such as alumina, magnesiumchloride or silica) or organic (such as a polymer or cross-linkedpolymer). Methods for the preparation of supported catalysts are knownin the art. Slurry, suspension, solution and high-pressure processes asknown to those skilled in the art may also be used with supportedcatalysts of the invention.

As stated herein, a solution process is specified for certain benefits,with the solution process being run at a temperature above 90° C., morespecifically at a temperature above 100° C., further more specificallyat a temperature above 110° C. and even further more specifically at atemperature above 130° C. Suitable solvents for polymerization arenon-coordinating, inert liquids. Examples include straight andbranched-chain hydrocarbons such as isobutane, butane, pentane,isopentane, hexane, isohexane, heptane, octane, Isopar-E® and mixturesthereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perhalogenated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, chlorobenzene, and aromatic and alkylsubstituted aromaticcompounds such as benzene, toluene, mesitylene, and xylene. Suitablesolvents also include liquid olefins which may act as monomers orcomonomers including ethylene, propylene, 1-butene, butadiene,cyclopentene, 1-hexene, 1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, isobutylene,styrene, divinylbenzene, allylbenzene, and vinyltoluene (including allisomers alone or in admixture). Mixtures of the foregoing are alsosuitable. Other additives that are useful in a polymerization reactionmay be employed, such as scavengers, promoters, etc.

In some embodiments, the molecular weight of the copolymers orinterpolymers are controlled by the amount of hydrogen present in thepolymerization reactor. Therefore, when ultra low molecular weightpolymers are desired, an excessive amount of hydrogen is used,especially for the substantially random polymers described herein. Inother embodiments, certain catalysts are selected such that only lowmolecular weight polymers are produced without the need for usinghydrogen as a molecular weight regulator. This is the case for theinterpolymers with vinyl end groups.

Applications

The low molecular weight polymers disclosed herein have many usefulapplications and can be used to make a multitude of articles ofmanufacture. The article of manufacture includes, but is not limited to,waxes, lubricants, additives, etc. The waxes may be used to formulatepaints and coatings, printing inks, carbon paper, photo toners, buildingand construction materials, mold release agents, hot melt adhesives,candles. The waxes may also be used in wood processing, metal working,powder metallurgy and sintering, wax modeling, sizing, crop protection,and so on. Due to the presence of the vinyl end groups, the lowmolecular weight polymers can be functionalized by reacting the polymerswith a reagent which can react with the vinyl group. Thus, variousfunctionalized low molecular weight polymers are obtained.

Waxes

The low molecular weight polymers disclosed herein can be used as a waxor a blend of waxes. The waxes or blends thereof are used to formulatehot melt adhesives, plastic additives, aqueous dispersions, processingaids, lubricants, printing inks, toners, etc. Methods and components formaking such products are disclosed, for example, in the following U.S.Pat. Nos. 6,143,846; 5,928,825; 5,530,054; 6,242,148; 6,207,748;5,998,547; 6,262,153; 5,037,874; 5,482,987; 6,133,490; and 6,080,902; inthe following PCT applications: WO 01/44387; WO 01/72855; WO 01/64776;WO 01/56721; WO 01/64799; WO 01/64800; in the following EP patents orpatent applications: EP 890619; EP 916700; and EP 0050313; EP 1081195;in the following German patents or patent applications: DE 10063422; DE10063423; DE 10063424; and DE 10063421; in the following Japanese PatentApplication No. 11228911 A2; and in the following Chinese patents orpatent applications: CN 1270187; and CN 1270189. The low molecularweight polymers disclosed herein can be used as a wax as taught in theabove patents or patent applications with or without modifications.

Additional wax applications are disclosed in the following U.S. Pat. No.6,060,550 entitled “Polyethylene wax as processing aid for hot-meltadhesive compositions;” U.S. Pat. No. 6,028,138 entitled “Phase changeink formulation using urethane isocyanate-derived resins, a polyethylenewax and toughening agent;” U.S. Pat. No. 5,994,453 entitled “Phasechange ink formulation containing a combination of a urethane resin, amixed urethane/urea resin, a mono-amide and a polyethylene wax;” U.S.Pat. No. 5,037,874 entitled “Hot melt system comprising a polyethylenewax with CO incorporated in the wax;” U.S. Pat. No. 6,331,590 entitled“Polypropylene wax;” U.S. Pat. No. 6,316,650 entitled “Wax preparationcomprising partial esters of polyols and montan wax acid and Ca soaps ofmontan wax acid; U.S. Pat. No. 6,303,665 entitled “Spray-resistantaqueous foam, its production and use;” U.S. Pat. No. 6,262,153 entitled“Colored wax articles;” U.S. Pat. No. 6,251,553 entitled “Use ofmixed-crystal pigments of the quinacridone series in electrophotographictoners and developers, powder coatings and inkjet inks;” U.S. Pat. No.6,117,922 entitled “Solid, storage-stable antistat mixtures and processfor their preparation;” U.S. Pat. No. 6,117,606 entitled “Use of pigmentyellow 155 in electrophotographic toners and developers, powder coatingsand inkjet inks;” U.S. Pat. No. 6,110,238 entitled “Process forimproving the cold-flow properties of fuel oils;” U.S. Pat. No.6,107,530 entitled “Use of polyolefin waxes in solvent pastes;”6,080,902 entitled “Method of using polyolefin waxes;” U.S. Pat. No.6,005,042 entitled “Aqueous polymer dispersions as binders for elastic,nonblocking and scratch-resistant coatings;” U.S. Pat. No. 5,998,547entitled “Polypropylene waxes modified so as to be polar;” U.S. Pat. No.5,840,416 entitled “Lining material, method for coating a material forproducing a lining, and apparatus;” U.S. Pat. No. 5,783,618 entitled“Aqueous wax and silicone dispersions, their production and use;” U.S.Pat. No. 5,494,593 entitled “Amphoteric surfactants-containing waxcompositions, their production and their use;” U.S. Pat. No. 4,357,185entitled “Process for coating crystalline explosives with polyethylenewax.” The low molecular weight polymers disclosed herein can be used asa wax as taught in the above patents with or without modifications. Forexample, the waxes made from the low molecular weight polymers can beused in textile applications in a manner disclosed in the following U.S.patents: U.S. Pat. No. 4,675,022, entitled “Aqueous wax dispersionsuseful as textile finishing agents;” U.S. Pat. No. 4,329,390, entitled“Cationic surfactant-containing aqueous wax dispersions, and their useas textile finishing agents;” and U.S. Pat. No. 4,165,603, entitled“Apparatus for waxing yarn using solid wax on a textile machine.” Suchwaxes can also be used to form wax dispersions as those disclosed thefollowing U.S. Pat. No. 6,075,090, entitled “Method of preparing annon-aqueous composite wax particle dispersion;” U.S. Pat. No. 6,066,316,entitled “Fine dispersion composition of wax, hair cosmetic preparationand glazing agent;” U.S. Pat. No. 5,798,136, entitled “Simultaneouscoatings of wax dispersion containing lubricant layer and transparentmagnetic recording layer for photographic element;” U.S. Pat. No.5,637,147, entitled “Calendar for producing a sheet havingwax-containing dispersion thereon.” Such waxes may also be used in themanner disclosed in the preceding patents. Some examples of theapplications are described as follows.

1) Hot Melt Adhesive

As an example, the low molecular weight polymers disclosed herein can beused as a wax component in a hot melt adhesive. Generally, hot meltadhesives comprise three components: a polymer, a tackifier, and a wax.Each component may comprise a blend of two or more components, that is,the polymer component may comprise a blend of two different polymers.The polymer provides cohesive strength to the adhesive bond. Thetackifier provides tack to the adhesive which serves to secure the itemsto be bonded while the adhesive sets, and reduces the viscosity of thesystem making the adhesive easier to apply to the substrate. Thetackifier may be further used to control the glass transitiontemperature of the formulation. The wax controls the open/close timesand reduces the viscosity of the system. Hot melt adhesives may furthertypically comprise oil as a filler and/or to reduce the viscosity of thesystem.

Hot melt adhesives based on previously used polymers include ethylenevinyl acetate copolymers (EVA), atactic polypropylene (APP), amorphouspolyolefins, low density polyethylene (LDPE), and homogeneous linearethylene/alpha-olefin copolymers. Prior art hot melt adhesives typicallyemployed large levels of tackifier to reduce the viscosity of the systemto levels which enabled its facile application to the substrate, forinstance, to viscosities less than about 5000 centipoise.

Pressure sensitive adhesives are materials which are aggressively andpermanently tacky at room temperature at the time of application, andwhich firmly adhere to a variety of dissimilar surfaces with theapplication of light pressure, such as pressing with a finger. Despitetheir aggressive tackiness, pressure sensitive adhesives may be removedfrom smooth surfaces without leaving significant residue. Pressuresensitive adhesives are widely used in everyday applications, such asmasking tape, clear office tape, labels, decals, bandages, decorativeand protective sheets (such as shelf and drawer liners), floor tiles,sanitary napkin/incontinence device placement strips, sun control films,and the joining of gaskets to automobile windows.

Historically, pressure sensitive adhesives were based on natural rubberand wood rosins, which were carried by a solvent. Articles bearing suchadhesives were manufactured by applying a solution of the adhesive on asuitable backing, and removing the solvent by a devolatilizing process.However, in response to cost increases in solvents and regulatoryrestrictions regarding emissions, water-based adhesives and solid-formhot melt adhesives (HMA's) have been developed.

Historically, adhesives have been based on one of four types ofpolymers: elastomers (such as natural rubber, styrene-isoprene-styreneblock copolymers, styrene-butadiene-styrene block copolymers, andstyrene-butadiene random copolymers); acrylics (such as interpolymers ofbutyl acrylate, 2-ethyl hexyl acrylate, and methyl methacrylate);hydrocarbons (such as a tactic polypropylene, amorphous polypropylene,poly-1-butene, and low density polyethylene); and ethylene vinylacetate. More recently, hot melt adhesives based on homogeneous linearand substantially linear ethylene polymers have been disclosed andclaimed.

Diene-based elastomers may be utilized in solvent-based, water-born, andhot melt adhesives. However, adhesive systems based on such elastomersare disadvantageous in that the sites of unsaturation in the blockcopolymer backbone make the hot melt adhesive susceptible to degradationby the action of oxygen and ultraviolet light.

Acrylic systems, while stable to oxygen and ultraviolet light areinferior to diene-based elastomer systems in terms of the balance oftack, peel and creep resistance which is preferred for pressuresensitive adhesive applications. Further, such systems are typicallyavailable only in the solvent-based and water-borne systems, making themfurther disadvantageous for the reasons set forth above.

Hydrocarbon-based systems were developed at least in part to provideimproved stability to oxygen and ultraviolet light, as compared todiene-based elastomer systems, as well as the ability to be utilized inhot melt adhesive systems. Hydrocarbon-based systems which comprise,atactic polypropylene, interpolymers of propylene with higher orderalpha-olefins, or poly-alpha-olefins, exhibit a poor balance ofproperties. In particular poly-1-butene has a tendency to slowlycrystallize after application to the substrate, leading to a profoundloss of tack. When oil is added to increase tack, the oil tends tomigrate out of the adhesive into the backing layer or the substrate.Atactic polypropylene and poly-alpha-olefins suffer from low tensilestrength, which leads to low cohesive strength on peel and to theleaving of a residue on the substrate surface after peeling.Hydrocarbon-based systems are typically not preferred due to the limitedability of low density polyethylene to accept the formulationingredients required to produce a hot melt adhesive with suitablemechanical properties.

Ethylene vinyl acetate based systems are limited in that as higher vinylacetate levels are selected, elastic performance increases, butcompatibility with formulation ingredients decreases.

Hot melt adhesives based on homogeneous linear ethylene/alpha-olefincopolymers are disclosed in U.S. Pat. No. 5,530,054.

In some embodiments, ultra-low molecular weight ethylene polymersdisclosed herein may be employed as an extending or modifyingcomposition. Ultra-low molecular weight polymers employed will be eitherethylene homopolymers or interpolymers of ethylene and a comonomerselected from the group consisting of C₃-C₂₀ alpha-olefins, styrene,alkyl-substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane,non-conjugated dienes, and cycloalkenes.

The ultra-low molecular weight polymer may have a number averagemolecular weight less than 8200, preferably less than 6000, and morepreferably less than 5000. Such ultra-low molecular weight polymer maytypically have a number average molecular weight of at least 800,preferably at least 1300.

Ultra-low molecular weight polymers, in contrast to paraffinic waxes andcrystalline ethylene homopolymer or interpolymer waxes, may have aM_(w)/M_(n) of from 1.5 to 2.5, preferably from 1.8 to 2.2.

Ultra-low molecular weight ethylene polymers generally lead to a lowpolymer and formulation viscosity, but are characterized by peakcrystallization temperatures which are greater than the peakcrystallization temperatures of corresponding higher molecular weightmaterials of the same density. In adhesive applications, the increase inpeak crystallization temperature translates to an increased heatresistance, for instance, an improved creep resistance in pressuresensitive adhesives, and improved shear adhesion failure temperature(SAFT) in hot melt adhesives.

When the ultra-low molecular weight ethylene polymer is an interpolymerof ethylene and at least one vinylidene aromatic comonomer or hinderedaliphatic vinylidene comonomer, it may be employed as a tackifier (asdescribed above). Further, as the mole percent of ethylene increases,the crystallinity of the interpolymer will likewise increase.Accordingly, ultra-low molecular weight interpolymers may be useful aswaxes to control the open and close time of the adhesive system.

In other embodiments, a traditional wax may be used as an extending ormodifying composition. Modification of the adhesive with a paraffinicwax or a crystalline polyethylene wax, will tend to improve the hightemperature performance, such as creep resistance and SAFT, and reducethe open and close times of adhesives comprising substantially randominterpolymers which have a high styrene content.

2) Toners

Polyethylene and polypropylene waxes made in some embodiments of theinvention can be used to make toners for use in image forming devices inaccordance with the disclosure of U.S. Pat. No. 6,242,148 and No.6,194,114. For example, the developing agent according to embodiments ofthe invention uses a binder resin having a glass transition pointbetween 50 and 65° C. and a 150° C. melt index between 1 and 10 (g/10min.). The use of a binder resin having these ranges of resincharacteristics allows the toner to be efficiently fixed to paper duringa fixing step. Such a resin also has the effect of precluding the tonerfrom being solidified during storage in a hot and humid environment.

A suitable resin material includes a copolymer of a styrene and itssubstitution product or an acrylic-based resin. The copolymer of astyrene and its substitution product includes, for example, apolystyrene homopolymer, a styrene resin with hydrogen addition,styrene-isobutylene copolymer, a styrene-butadiene copolymer, anacrylonitrile-butadiene-styrene three-component copolymer, anacrylonitrile-styrene-acrylic ester three-component copolymer, astyrene-acrylonitrile copolymer, an acrylonitrile-acrylic rubber-styrenethree-component copolymer, an acrylonitrile-EVA-styrene three-componentcopolymer, a styrene-p-chlorostyrene copolymer, a styrene-propylenecopolymer, a styrene-butadiene rubber, or a styrene-maleic anhydride.

In addition, the acrylic-based resin includes, for example, apolyacrylate, a polymethylmethacrylate, a polyethylmethacrylate, apoly-n-butylmethacrylate, a polyglycidylmethacrylate, polycondensedfluorine acrylate, a styrene-methacrylate copolymer, astyrene-butylmethacrylate copolymer, or a styrene-acrylic ethylcopolymer. Other suitable binder resins include a polyvinyl chloride, apolyvinyl acetate, a polyethylene, a polypropylene, a polyester, apolyurethane, a polyamide, an epoxy resin, a phenol resin, a urea resin,a polyvinyl butyral, a polyacrylic resin, a rosin, a modified rosin, aterpen resin, an aliphatic or alicylic hydrocarbon resin, an aromaticpetroleum resin, a chlorinated paraffin, and a paraffin wax, which areused in a unitary or mixed form.

A suitable charge control agent includes an alloy azo dye, for example,“Bali First Black 3804”, “Pontron S-31”, “Pontron S-32”, “Pontron S-32”,“Pontron S-34”, “Pontron S-36” (manufactured by Orient Chemical Co.,Ltd.), “Aizen Spiron Black TRH”, “T-95”, “T-77” (manufactured byHodogaya Chemical Co., Ltd.), an metal complex of an alkyl derivative ofsalicylate, for example, “Pontron E-82”, “Pontron E-84”, “Pontron E-85”(manufactured by Orient Chemical Co., Ltd.), and metal-free “TN-105”(manufactured by Hodogaya Co., Ltd.). A suitable coloring agent includesa carbon black or an organic or inorganic pigment or dye. The carbonblack includes, but not limited to, a thermal black, an acetylene black,a channel black, a furnace black, a lamp black, or a kitchen black, forexample.

Polypropylene and polyethylene are used as a parting agent. Thepolypropylene wax has a melting point between 135 and 160° C. and isadded in 3 to 6 percent by weight. The polyethylene wax can be added ata temperature between 90 and 180° C. and can be present in 1 to 3percent by weight of the total composition.

An additive that can be added to the toner according to embodiments ofthe invention includes silica grains, metallic oxide grains, andcleaning auxiliaries. The silica grains include a silicon dioxide, analuminum silicate, a sodium silicate, a zinc silicate, and a magnesiumsilicate.

The metallic oxide grains include an zinc oxide, a titanium oxide, analuminum oxide, an zirconium oxide, a strontium titanate, and a bariumtitanate. The cleaning auxiliaries include resin powders such as apolymethylmethacrylate, a polyvinylidene fluoride, and apolytetrafluoroethylene. These external additives may be subjected tosurface treatment such as hydrophobicity treatment.

A method for manufacturing the toner according to embodiments of theinvention is described below. First, the binder resin, the coloringagent, the waxes, the charge control agent, and other components asrequired are dispersed and mixed together using a ball mill, aV-blender, a Nauta mixer, or a Henshel mixer. Next, the mixture obtainedis melted and kneaded under heat using a pressure kneader, a roll, ascrew extruder, or a banbury mixer. Subsequently, the kneaded mixture iscoarsely crushed using a hammer mill, a crusher mill, or a jet mill.Further, the coarsely crushed mixture is pulverized using the jet mill,and the resulting mixture is then classified into desired particle sizesby means of air separation or the like. Finally, a predeterminedadditive is added to the mixture and mixed therewith using a high-speedfluidized blender to obtain a desired toner. This high-speed fluidizedblender includes, for example, a Henshel mixer, a super mixer, and amicrospeed mixer.

3) Investment Casting

The wax composition in accordance with embodiments of the invention canbe used in investment casting, also known as precision casting.Investment casting involves introducing molten metal into molds madefrom refractory materials, such as ceramics. Slurries containingrefractory material and other materials, such as binders, dispersingaids, etc., are formed. A pattern formed from a wax composition isimmersed in a first slurry, which deposits refractory material on thepattern's surface. Stucco material is applied to the refractorymaterial. The first such layer applied to the pattern is referred to asthe facecoat, and contacts the metal during the casting process. Pluraladditional layers are then applied to the pattern to form the mold. Thepattern is removed from inside the mold by heating the mold/patterncomposite. Removing the pattern forms an internal void in the moldhaving the shape of the desired article. Molten metal is poured into thevoid and allowed to solidify. The mold is then removed from about thearticle.

Pattern wax compositions used in conventional casting processestypically include significant amounts of filler materials, such as atleast 30 percent filler. Examples of conventional fillers include ureaand water. Fillers are added to the wax compositions for a number ofreasons, including to reduce the amount of wax used, and to changecertain physical properties of the wax composition, such as shrinkage.

Pattern wax and wax fillers generally are partially or totally removedfrom the mold prior to pouring metal. Wax and wax fillers typically areremoved from the mold by first autoclaving the mold/pattern composite,followed by firing under oxygen-rich environments to remove anyremaining residues. Certain known fillers, such as acrylates, aredifficult to burn completely. Additional information concerninginvestment casting is disclosed in the following U.S. patents: U.S. Pat.No. 5,651,932, entitled “Method for investment wax casting of golf clubheads;” U.S. Pat. No. 5,518,537 entitled “Filler and wax composition forinvestment casting;” U.S. Pat. No. 5,372,177 entitled “Method andapparatus for removing wax from casting mold;” U.S. Pat. No. 5,006,583entitled “Filler and wax composition for investment casting;” U.S. Pat.No. 4,978,452 entitled “Method for producing wax impregnated filters forinvestment casting applications;” U.S. Pat. No. 4,934,921 entitled“Investment casting wax injection machine;” U.S. Pat. No. 4,144,075entitled “Wax composition for investment casting and casting method”.The wax composition disclosed herein can be used in a manner taught inthe preceding patents.

In addition to investment casting, the wax composition in accordancewith embodiments of the invention can be used as a binder for metal andceramic powder for powder injection molding. Such processes aredisclosed in the following U.S. patents: U.S. Pat. No. 6,051,184,entitled “Metal powder injection moldable composition, and injectionmolding and sintering method using such composition;” U.S. Pat. No.5,950,063, entitled “Method of powder injection molding;” U.S. Pat. No.5,427,734, entitled “Process for preparing R—Fe—B type sintered magnetsemploying the injection molding method;” U.S. Pat. No. 5,421,853,entitled “High performance binder/molder compounds for making precisionmetal part by powder injection molding;” U.S. Pat. No. 5,417,756,entitled “Process and molding compound for producing inorganic sinteredproducts by injection molding;” U.S. Pat. No. 5,095,048 Method ofmanufacturing a composition for use in injection molding powdermetallurgy;” U.S. Pat. No. 5,080,714, entitled “Compound for aninjection molding”.

Lubricants or Oil Additives

The low molecular weight polymers disclosed herein may also be used tomake lubricants or be used as oil additives. Both copolymers andterpolymers can be used. An example of copolymer is ethylene-styrenecopolymer or interpolymer; an example of terpolymer isethylene-propylene-styrene terpolymer. The polymers disclosed herein canbe used to replace one of more components of the lubricants or oilcompositions disclosed in the following U.S. patents: U.S. Pat. No.6,310,164 entitled “Unsaturated copolymers, processes for preparing thesame, and compositions containing the same;” U.S. Pat. No. 6,110,880entitled “Polyolefin block copolymer viscosity modifier;” U.S. Pat. No.6,100,224 entitled “Copolymers of ethylene alpha-olefin macromers anddicarboxylic monomers and derivatives thereof, useful as additives inlubricating oils and in fuels;” U.S. Pat. No. 6,084,046 entitled“Copolymer and copolymer composition;” U.S. Pat. No. 6,030,930 entitled“Polymers derived from ethylene and 1-butene for use in the preparationof lubricant disperant additives;” U.S. Pat. No. 6,017,859 entitled“Polymers derived from olefins useful as lubricant and fuel oiladditives, processes for preparation of such polymers and additives anduse thereof;” U.S. Pat. No. 5,912,212 entitled “Lubricating oilcomposition;” U.S. Pat. No. 5,811,379 entitled “Polymers derived fromolefins useful as lubricant and fuel oil additives, processes forpreparation of such polymers and additives and use thereof (PT-1267);”U.S. Pat. No. 5,759,967 entitled “Ethylene alpha-olefin/dieneinterpolymer-substituted carboxylic acid dispersant additives;” U.S.Pat. No. 5,747,596 entitled “Gel-free alpha-olefin dispersant additivesuseful in oleaginous compositions;” U.S. Pat. No. 5,717,039 entitled“Functionalization of polymers based on Koch chemistry and derivativesthereof;” U.S. Pat. No. 5,663,129 entitled “Gel-free ethyleneinterpolymer dispersant additives useful in oleaginous compositions;”U.S. Pat. No. 5,658,865 entitled “Oxidation-inhibitive lubricating oilcomposition;” U.S. Pat. No. 5,366,647 entitled “Derivatized ethylenealpha-olefin polymer useful as multifunctional viscosity index improveradditive for oleaginous composition (PT-796);” U.S. Pat. No. 5,294,234entitled “Fuel compositions of novel ethylene alpha-olefin polymerssubstituted amine dispersant additives;” U.S. Pat. No. 5,277,833entitled “Ethylene alpha-olefin polymer substituted mono- anddicarboxylic acid lubricant dispersant additives;” U.S. Pat. No.5,275,747 entitled “Derivatized ethylene alpha-olefin polymer useful asmultifunctional viscosity index improver additive for oleaginouscomposition;” U.S. Pat. No. 5,229,022 entitled “Ethylene alpha-olefinpolymer substituted mono- and dicarboxylic acid dispersant additives(PT-920);” and U.S. Pat. No. 5,017,299 entitled “Novel ethylenealpha-olefin copolymer substituted Mannich base lubricant dispersantadditives”.

Lubricating Oils

A variety of lubricant compositions or lubricating oils can beformulated using the low molecular weight polymers disclosed herein. Forexample, a lubricating oil composition can comprise thealpha-olefin/aromatic vinyl monomer random copolymer disclosed hereinand a lubricating oil additive. When the alpha-olefin/aromatic vinylmonomer random copolymer is used as a lubricating base oil and blendedwith at least one additive, such as an extreme pressure agent, anabrasion resistance agent, an oiliness improver and adetergent-dispersant, a lubricating oil composition having excellentproperties can be obtained.

In addition, another lubricating oil composition can comprise: (1) abase oil comprising a mineral oil and/or a hydrocarbon synthetic oil,and (2) an alpha-olefin/aromatic vinyl monomer random copolymer whichcomprises 40 to 75 percent by mol of constituent units derived fromethylene, 0 to 45 percent by mol of constituent units derived from analpha-olefin of 3 to 20 carbon atoms and 1 to 40 percent by mol ofconstituent units derived from an aromatic vinyl monomer, with theproviso that the total amount of the constituent units derived fromethylene and the constituent units derived from the alpha-olefin is 60to 99 percent by mol, and has an intrinsic viscosity [η], as measured indecalin at 135° C., of 0.1 to 5.0 dl/g.

Still another lubricating oil composition comprises: (1) a base oilcomprising a mineral oil and/or a hydrocarbon synthetic oil, (2) alow-molecular weight alpha-olefin/aromatic vinyl monomer randomcopolymer which comprises 40 to 75 percent by mol of constituent unitsderived from ethylene, 0 to 45 percent by mol of constituent unitsderived from an alpha-olefin of 3 to 20 carbon atoms and 1 to 40 percentby mol of constituent units derived from an aromatic vinyl monomer, withthe proviso that the total amount of the constituent units derived fromethylene and the constituent units derived from the alpha-olefin is 60to 99 percent by mol, and has an intrinsic viscosity [η], as measured indecalin at 135° C., of 0.01 to 0.30 dl/g, and (3) a lubricating oiladditive.

A viscosity index improver can be formulated according to embodiments ofthe invention. It comprises the same alpha-olefin/aromatic vinyl monomerrandom copolymer as the specific alpha-olefin/aromatic vinyl monomerrandom copolymer employable in the second lubricating oil composition.Similarly, a lubricating oil compatibility improver can be formulatedaccording to embodiments of the invention. It comprises the samelow-molecular weight alpha-olefin/aromatic vinyl monomer randomcopolymer as the specific low-molecular weight alpha-olefin/aromaticvinyl monomer random copolymer employable in the third lubricating oilcomposition.

A fuel oil composition can also be prepared according to embodiments ofthe invention comprises: (1) a middle fraction fuel oil having a boilingpoint of 150 to 400° C., and (2) an alpha-olefin/aromatic vinyl typefuel oil fluidity improver comprising an alpha-olefin/aromatic vinylmonomer random copolymer which comprises 60 to 90 percent by mol ofconstituent units derived from ethylene, 0 to 39 percent by mol ofconstituent units derived from an alpha-olefin of 3 to 20 carbon atomsand 1 to 40 percent by mol of constituent units derived from an aromaticvinyl monomer, with the proviso that the total amount of the constituentunits derived from ethylene and the constituent units derived from thealpha-olefin is 60 to 99 percent by mol, and has an intrinsic viscosity[η], as measured in decalin at 135° C., of 0.01 to 1.0 dl/g.

A. Lubricating Oil Additive

The lubricating oil additive for use in embodiments of the invention isat least one additive selected from an extreme pressure agent, anabrasion resistance agent, an oiliness improver and adetergent-dispersant.

Examples of the extreme pressure agents include sulfur type extremepressure agents, such as sulfides, sulfoxides, sulfones,thiophosphinates, thiocarbonates, fats and oils, sulfurized fats andoils, and olefin sulfides; phosphoric acids, such as phosphoric esters,phosphorous esters, phosphoric ester amines and phosphorous esteramines; and halogen compounds, such as chlorinated hydrocarbons.

Examples of the abrasion resistance agent include inorganic or organicmolybdenum compounds, such as molybdenum disulfide; organoboroncompounds, such as alkylmercaptyl borate; graphite; antimony sulfide;boron compounds; and polytetrafluoroethylene.

Examples of the oiliness improvers include higher fatty acids, such asoleic acid and stearic acid; higher alcohols, such as oleyl alcohol;amines; esters; sulfurized fats and oils; and chlorinated fats and oils.

Examples of the detergent-dispersants include metallic sulfonates, suchas calcium sulfonate, magnesium sulfonate and barium sulfonate;thiophosphonates; phenates; salicylates; succinimides; benzylamine; andsuccinates.

The lubricating oil composition may further contain a viscosity indeximprover, an antioxidant, an anti-corrosion agent and an anti-foamingagent.

As the viscosity index improvers, those generally added to lubricatingoils are available, and examples thereof include natural resins, such asmineral oil, and synthetic resins, such as ethylene/alpha-olefincopolymer, alpha-olefin homopolymer, styrene/butadiene copolymer,poly(meth)acrylate and naphthalene condensate.

Examples of the antioxidants include amine compounds, such as2,6-di-t-butyl-4-methylphenol; and sulfur or phosphorus compounds, suchas zinc dithiophosphate.

Examples of the anti-corrosion agents include carboxylic acids and theirsalts, such as oxalic acid; sulfonates; esters; alcohols; phosphoricacid and its salts; benzotriazole and its derivatives; and thiazolecompounds.

Examples of the anti-foaming agents include silicone compounds, such asdimethylsiloxane and silica gel dispersion; alcohol compounds; and estercompounds.

Though the amount of the lubricating oil additive used varies dependingon the lubricating properties requested, it is in the range of usually0.01 to 80 parts by weight, preferably 0.05 to 60 parts by weight, basedon 100 parts by weight of the alpha-olefin/aromatic vinyl compoundrandom copolymer.

The lubricating oil composition may further contain a mineral oil or ahydrocarbon synthetic oil in an amount of up to 50 percent by weight.

Since the lubricating oil composition contains the alpha-olefin/aromaticvinyl compound random copolymer as a base oil, the composition isexcellent in compatibility with additives as well as in viscosityproperties, heat stability, oxidation stability and abrasion resistance.

B. Base Oil

The base oil used in the second lubricating oil composition is alubricating base oil comprising a mineral oil and/or a hydrocarbonsynthetic oil. These oils can be used alone or as a mixture of two ormore kinds without specific limitation, as long as they have a viscosityat 100° C. of 1.5 to 40.0 mm²/S, preferably 2.0 to 10.0 mm²/S. Themineral oil has a viscosity in the above range.

The mineral oil is, for example, a refined oil obtained by subjecting aparaffin base crude oil or an intermediate base crude oil to atmosphericdistillation or subjecting a residual oil of the atmosphericdistillation to vacuum distillation and then refining the resultingdistillate oil in a conventional manner, or a deep-dewaxed oil obtainedby deep-dewaxing the refined oil obtained above. Examples of therefining methods include hydrogenation, dewaxing, solvent extraction,alkali distillation, sulfuric acid washing and clay treatment. Thesemethods can be carried out singly or in appropriate combination, or thesame method can be repeated plural times. In these cases, there is nospecific limitation on the order of the methods and the number ofrepetition times. In the present invention, it is particularlypreferable to use a mineral oil obtained by a solvent dewaxing processthat is made under severe conditions or obtained by a deep-dewaxingprocess such as a catalytic hydrogenation dewaxing process using azeolite catalyst.

Examples of the hydrocarbon synthetic oils preferably used includeoligomers obtained by polymerizing or copolymerizing olefins of 2 to 20carbon atoms or arbitrary mixtures of these olefins, such as an oligomerof 1-octene, an oligomer of 1-decene and an oligomer of 1-dodecene. Inaddition to the mineral oil and/or the hydrocarbon synthetic oil, alsoavailable are diesters, such as di-2-ethylhexyl sebacate, dioctyladipate and dioctyl dodecanoate, and polyol esters, such aspentaerythritol tetraoleate and trimethylolpropane tripelargonate. Theoligomers are obtained by (co)polymerizing olefins of 2 to 20 carbonatoms by any processes. In the second lubricating oil composition, thebase oil is used in an amount of 50.0 to 99.8 percent by weight,preferably 60.0 to 95.0 percent by weight.

C. Other Additives

Additive concentrates and lubricating oil compositions disclosed hereinmay contain other additives. The use of such additives is optional andthe presence thereof in the compositions will depend on the particularuse and level of performance required. Thus the other additive may beincluded or excluded. Additive concentrates typically comprise from 0.1percent to 30 percent by weight of interpolymer and from 70 percent to99.9 percent by weight of a substantially, inert, normally liquid,organic diluent.

Lubricating oil compositions often comprise zinc salts of adithiophosphoric 15 acid, often referred to as zinc dithiophosphates,zinc 0,0-dihydrocarbyl dithiophosphates, and other commonly used names.They are sometimes referred to by the abbreviation 2DP. One or more zincsalts of dithiophosphoric acids may be present in a minor amount toprovide additional extreme pressure, anti-wear and anti-oxidancyperformance.

Other additives that may optionally be used in the lubricating oils ofthis invention include, for example, detergents, dispersants,supplemental viscosity improvers, oxidation inhibiting agents, corrosioninhibiting agents, pour point depressing agents, extreme pressureagents, anti-wear agents, color stabilizers, friction modifiers, andanti-foam agents.

Extreme pressure agents and corrosion and oxidation inhibiting agentswhich may be included in the compositions of the invention areexemplified by chlorinated aliphatic hydrocarbons, organic sulfides andpolysulfides, phosphorus esters including dihydrocarbon andtrihydrocarbon phosphites, molybdenum compounds, and the like.

Other oxidation inhibiting agents include materials such as alkylateddiphenyl amines, hindered phenols, especially those having tertiaryalkyl groups such as tertiary butyl groups in the position ortho to thephenolic —OH group, and others. Such materials are well known to thoseof skill in the art.

Auxiliary viscosity improvers (also sometimes referred to as viscosityindex improvers or viscosity modifiers) may be included in thecompositions of this invention. Viscosity improvers are usuallypolymers, including polyisobutenes, polymethacrylic acid esters,hydrogenated diene polymers, polyalkyl styrenes, esterifiedstyrene-maleic anhydride copolymers, hydrogenatedalkenylarene-conjugated diene copolymers and polyolefins.

Multifunctional viscosity improvers, which also have dispersant and/orantioxidancy properties are known and may optionally be used in additionto the products of this invention. Pour point depressants may beincluded in the additive concentrates and lubricating oils describedherein. Those which may be used are described in the literature and arewell-known to those skilled in the art; see for example, page 8 of“Lubricant Additives” by C. V. Smalheer and R. Kennedy Smith(Lezius-Riles Company Publisher, Cleveland, Ohio, 1967). Pour pointdepressants useful for the purpose of this invention, techniques fortheir preparation and their use are described in U.S. Pat. Nos.2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 30 2,666,748;2,721,877; 2,721,878; 3,250,715; and 5,707,943.

Anti-foam agents used to reduce or prevent the formation of stable foaminclude silicones or organic polymers. Examples of these and additionalanti-foam compositions are described in “Foam Control Agents”, by HenryT. Kemer (Noyes Data Corporation, 1976), pages 125-162. Detergents anddispersants may be of the ash-producing or ashless type. Theash-producing detergents are exemplified by oil soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids,carboxylic acids, phenols or organic phosphorus acids characterized by aleast one direct carbon-to-phosphorus linkage.

The term “basic salt” is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. The relative amount of metal present in “basic salts” isfrequently indicated by the expression “metal ratio” (abbreviated MR),which is defined as the number of equivalents of metal present comparedto a “normal”, stoichiometric amount. Thus, for example, a basic saltcontaining twice the amount of metal compared to the stoichiometricamount, has a metal ratio (MR) of 2.

Ashless detergents and dispersants are so-called despite the fact that,depending on its constitution, the detergent or dispersant may uponcombustion yield a nonvolatile residue such as boric oxide or phosphoruspentoxide; however, it does not ordinarily contain metal and thereforedoes not yield a metal-containing ash on combustion. Many types areknown in the art, and any of them are suitable for use in the lubricantsof this invention. The following are illustrative:

-   (1) Reaction products of carboxylic acids (or derivatives thereof)    containing at least about 34 and preferably at least about 54 carbon    atoms with nitrogen containing compounds such as amine, organic    hydroxy compounds such as phenols and alcohols, and/or basic    inorganic materials. Examples of these “carboxylic dispersants” are    described in British Patent number 1,306,529 and in many U.S.    patents including the following: U.S. Pat. Nos. 3,163,603;    3,399,141; 3,574,101; 3,184,474; 3,415,750; 3,576,743; 3,215,707;    3,433,744; 3,630,904; 3,219,666; 3,444,170; 3,632,510; 3,271,310;    3,448,048; 3,632,511; 3,272,746; 3,448,049; 3,697,428; 3,281,357;    3,451,933; 3,725,441; 3,306,908; 3,454,607; 4,194,886; 3,311,558;    3,467,668; 4,234,435; 3,316,177; 3,501,405; 4,491,527; 3,340,281;    3,522,179; 5,696,060; 3,341,542; 3,541,012; 5,696,067; 3,346,493;    3,541,678; 5,779,742; 3,351,552; 3,542,680; RE 26,433; 3,381,022;    and 3,567,637.-   (2) Reaction products of relatively high molecular weight aliphatic    or alicyclic halides with amines, preferably polyalkylene    polyamines. These may be characterized as “amine dispersants” and    examples thereof are described for example, in the following U.S.    patents: U.S. Pat. Nos. 3,275,554; 3,454,555; 3,438,757; and    3,565,804.-   (3) Reaction products of alkyl phenols in which the alkyl groups    contains at least about 30 carbon atoms with aldehydes (especially    formaldehyde) and amines (especially polyalkylene polyamines), which    may be characterized as “Mannich dispersants”. The materials    described in the following U.S. patents are illustrative: U.S. Pat.    Nos. 3,413,347; 3,725,480; 3,697,574; 3,726,882; and 3,725,277.-   (4) Products obtained by post-treating the carboxylic amine or    Mannich dispersants with such reagents as urea, thiourea, carbon    disulfide, aldehydes, ketones, carboxylic acids,    hydrocarbon-substituted succinic anhydrides, nitriles, epoxides,    boron compounds, phosphorus compounds or the like. Exemplary    materials of this kind are described in the following U.S. patents:    U.S. Pat. Nos. 3,036,003; 3,282,955; 3,493,520; 3,639,242;    3,087,936; 3,312,619; 3,502,677; 3,649,229; 3,200,107; 3,366,569;    3,513,093; 3,649,659; 3,216,936; 3,367,943; 3,533,945; 3,658,836;    3,254,025; 3,373,111; 3,539,633; 3,697,574; 3,256,185; 3,403,102;    3,573,010; 3,702,757; 3,278,550; 3,442,808; 3,579,450; 3,703,536;    3,280,234; 3,455,831; 3,591,598; 3,704,308; 3,281,428; 3,455,832;    3,600,372; 3,708,522; and 4,234,435.-   (5) Polymers and copolymers of oil-solubilizing monomers such as    decyl methacrylate, vinyl decyl ether and high molecular weight    olefins with monomers containing polar substituents, for example,    aminoalkyl acrylates or methacrylates, acrylamides and    poly-(oxyethylene)-substituted acrylates. These may be characterized    as “polymeric dispersants” and examples thereof are disclosed in the    following U.S. patents: U.S. Pat. Nos. 3,329,658; 3,666,730;    3,449,250; 3,687,849; 3,519,565; and 3,702,300.

The above-illustrated other additives may each be present in lubricatingcompositions at a concentration of as little as 0.001 percent by weight,usually ranging from 0.01 percent to 20 percent by weight. In mostinstances, they each contribute from 0.1 percent to 10 percent byweight, more often up to about 5 percent by weight.

D. Additive Concentrates

The various additive-compositions of this invention described herein canbe added directly to the oil of lubricating viscosity. Preferably,however, they are diluted with a substantially inert, normally liquidorganic diluent such as mineral oil, a synthetic oil such as apolyalphaolefin, naphtha, benzene, toluene or xylene, to form anadditive concentrate. These concentrates usually comprise 0.1 to 30percent by weight, frequently from 1 percent to 20 percent by weight,more often from 5 percent to 15 percent by weight, of the interpolymersof this invention and may contain, in addition, one or more otheradditives known in the art or described hereinabove. Additiveconcentrates are prepared by mixing together the desired components,often at elevated temperatures, usually less than 150° C., often no morethan about 130° C., frequently no more than about 115° C.

E. Oil of Lubricating Viscosity

The lubricating compositions of this invention employ an oil oflubricating viscosity, including natural or synthetic lubricating oilsand mixtures thereof. Mixture of mineral oil and synthetic oils,particularly polyalphaolefin oils and polyester oils, are often used.Natural oils include animal oils and vegetable oils (for example castoroil, lard oil and other vegetable acid esters) as well as minerallubricating oils such as liquid petroleum oils and solvent-treated oracid treated mineral lubricating oils of the paraffinic, naphthenic ormixed paraffinic-naphthenic types. Hydrotreated or hydrocracked oils areincluded within the scope of useful oils of lubricating viscosity.

Oils of lubricating viscosity derived from coal or shale are alsouseful. Synthetic lubricating oils include hydrocarbon oils andhalosubstituted hydrocarbon oils such as polymerized andinterpolymerized olefins. etc. and mixtures thereof, alkylbenzenes,polyphenyl. (for example, biphenyls, terphenyls, alkylated polyphenyls,etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides andtheir derivatives, analogs and homologues thereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof, andthose where terminal hydroxyl groups have been modified byesterification, esterification, etc., constitute other classes of knownsynthetic lubricating oils that can be used.

Another suitable class of synthetic lubricating oils that can be usedcomprises the esters of dicarboxylic acids and those made from C₅ to C₁₂monocarboxylic acids and polyol s or polyether polyols.

Other synthetic lubricating oils include liquid esters ofphosphorus-containing acids, polymeric tetrahydrofurans, alkylateddiphenyloxides and the like.

Unrefined, refined and re-refined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedherein above can used in the compositions of the present invention.Unrefined oils are those obtained directly from a natural or syntheticsource without further purification treatment. Refined oils are similarto the unrefined oils except they have been further treated in one ormore purification steps to improve one or more properties. Re-refinedoils are obtained by processes similar to those used to obtain refinedoils applied to refined oils which have been already used in service.Such re-refined oils often are additionally processed by techniquesdirected to removal of spent additives and oil breakdown products.

Specific examples of the above-described oils of lubricating viscosityare given in Chamberlin III, U.S. Pat. No. 4,326,972 and European PatentPublication 107,282. A basic, brief description of lubricant base oilsappears in an article by D. V. Brock, “Lubrication Engineering”, Volume43, pages 184-5, March, 1987.

Functionalization

The low molecular weight polymers disclosed herein may be modified bytypical grafting, hydrogenation, functionalizing, or other reactionswell known to those skilled in the art. The polymers may be readilysulfonated or chlorinated to provide functionalized derivativesaccording to established techniques.

The low molecular weight polymers disclosed herein may also be modifiedby various chain extending or cross-linking processes including, but notlimited to peroxide-, silane-, sulfur-, radiation-, or azide-based curesystems. A full description of the various cross-linking technologies isdescribed in U.S. Pat. No. 5,869,591 and No. 5,977,271.

Dual cure systems, which use a combination of heat, moisture cure, andradiation steps, may be effectively employed. Dual cure systems aredisclosed in U.S. Pat. No. 5,911,940 and No. 6,124,370. For instance, itmay be desirable to employ peroxide crosslinking agents in conjunctionwith silane crosslinking agents, peroxide crosslinking agents inconjunction with radiation, sulfur-containing crosslinking agents inconjunction with silane crosslinking agents, etc.

The low molecular weight polymers disclosed herein may also be modifiedby various other cross-linking processes including, but not limited tothe incorporation of a diene component as a termonomer in itspreparation and subsequent cross linking by the aforementioned methodsand further methods including vulcanization via the vinyl group usingsulfur for example as the cross linking agent.

The functionalization can occur at the terminal unsaturated group (forexample, vinyl group) or at the aromatic unsaturation. Functionalizationincludes, but is not limited to, hydrogenation, halogenation (such aschlorination), ozonation, hydroxylation, sulfonation, carboxylation,epoxidation, grafting, etc. Any functional groups, such as maleicanhyride, halogen, amine, amide, ester, carboxylic acid, ether, silane,siloxane, and so on, can be attached to the low molecular weightpolymers via known or unknown chemistry. For example, the low molecularweight polymers disclosed herein can be functionalized by the methodsdisclosed in the following U.S. patents or U.S. statutory inventionregistration: U.S. Pat. No. 5,849,828 entitled “Metalation andfunctionalization of polymers and copolymers;” U.S. Pat. No. 5,814,708entitled “Process for oxidative functionalization of polymers containingalkylstyrene;” U.S. Pat. No. 5,717,039 entitled “Functionalization ofpolymers based on Koch chemistry and derivatives thereof;” H1,064entitled “Melt functionalization of polymers.”

In some embodiments, functionalized products can be made using a phenolor substituted phenol, maleic anhydride, an epoxidizing agent, ahydrosilylating agent or carbon monoxide and hydrogen, and the like. Thelow molecular weight polymers disclosed herein may be chlorinated withany of a variety of reagents including elemental chlorine and thechlorinated product then reacted with any of a variety of amines, forexample ethylene diamine, to obtain aminated product useful in fuel andmotor oil compositions. See, for example, U.S. Pat. Nos. 3,960,515;4,832,702; 4,234,235; and WO 92/14806. Sulfonation can be conductedaccording to the methods disclosed in the following U.S. patents: U.S.Pat. No. 5,753,774 entitled “Functional group terminated polymerscontaining sulfonate group via sulfonation of ethylenically unsaturatedpolymers;” U.S. Pat. No. 5,723,550 entitled “Bulk sulfonation of EPDMrubber;” U.S. Pat. No. 5,596,128 entitled “Sulfonating agent andsulfonation process;” U.S. Pat. No. 5,030,399 entitled “Method ofin-mold sulfonation of molded plastic article;” U.S. Pat. No. 4,532,302entitled “Process for the sulfonation of an elastomeric polymer;” U.S.Pat. No. 4,308,215 entitled “Sulfonation process;” U.S. Pat. No.4,184,988 entitled “Process for the sulfonation of an elastomericpolymer;” U.S. Pat. No. 4,157,432 entitled “Bulk sulfonation process;”U.S. Pat. No. 4,148,821 entitled “Process for sulfonation.”

In accordance with some embodiments of this invention, the low molecularweight polymers with unsaturation (hereinafter “the unsaturatedalpha-olefin polymer”) is functionalized, for example, with carboxylicacid producing moieties (preferably acid or anhydride moieties)selectively at sites of carbon-to-carbon unsaturation on the polymerchains, either before or after or while simultaneously reacting thepolymer with monounsaturated carboxylic reactant, for example, maleicanhydride, preferably in the presence of a free-radical initiator, torandomly attach carboxylic acid producing moieties, that is, acid oranhydride or acid ester moieties, onto the polymer chains.

The unsaturated alpha-olefin polymer may be functionalized, for example,with carboxylic acid producing moieties (preferably acid or anhydride)by reacting the polymer under conditions that result in the addition offunctional moieties, that is, acid, anhydride, ester moieties, etc.,onto the polymer chains primarily, and preferably only, at sites ofcarbon-to-carbon unsaturation (also referred to as ethylenic or olefinicunsaturation).

In one embodiment, this selective functionalization can be accomplishedby halogenating for example, chlorinating or brominating the unsaturatedalpha-olefin polymer to 1 to 8 wt. percent, preferably 3 to 7 wt.percent chlorine, or bromine, based on the weight of polymer, by passingthe chlorine or bromine through the polymer at a temperature of 60° to250° C., preferably 110° to 160° C., for example, 120° to 140° C., for0.5 to 10, preferably 1 to 7 hours. The halogenated polymer is thenreacted with sufficient monounsaturated reactant capable of addingfunctional moieties the polymer, for example, monounsaturated carboxylicreactant, at 100 to 250° C., usually 180° C. to 235° C., for 0.5 to 10,for example, 3 to 8 hours, such that the product obtained will containthe desired number of moles of the monounsaturated carboxylic reactantper mole of the halogenated polymer. Processes of this general type aretaught in U.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.Alternatively, the polymer and the monounsaturated carboxylic reactantare mixed and heated while adding chlorine to the hot material.Processes of this type are disclosed in U.S. Pat. Nos. 3,215,707;3,231,587; 3,912,764; 4,110,349; 4,234,435; and in U.K. 1,440,219.

The preferred monounsaturated reactants that are used to functionalizethe unsaturated alpha-olefin polymer comprise mono- and dicarboxylicacid material, that is, acid, anhydride or acid ester material,including (i) monounsaturated C₄ to C₁₀ dicarboxylic acid wherein (a)the carboxyl groups are vicinal, (that is, located on adjacent carbonatoms) and (b) at least one, preferably both, of said adjacent carbonatoms are part of said mono unsaturation; or (ii) derivatives of (i)such as anhydrides or C₁ to C₅ alcohol derived mono- or diesters of (i).Upon reaction with the polymer, the monounsaturation of themonounsaturated carboxylic reactant becomes saturated. Thus, forexample, maleic anhydride becomes polymer substituted succinicanhydride, and acrylic acid becomes polymer substituted propionic acid.Exemplary of such monounsaturated carboxylic reactants are fumaric acid,itaconic acid, maleic acid, maleic anhydride, chloromaleic acid,chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid,cinnamic acid, and lower alkyl (for example, C₁ to C₄ alkyl) acid estersof the foregoing, for example, methyl maleate, ethyl fumarate, methylfumarate, etc.

The monounsaturated carboxylic reactant, preferably maleic anhydride,typically will be used in an amount ranging from about 0.01 percent toabout 10 percent, preferably 0.1 to 2.0 percent, based on the weight ofthe polymer.

While chlorination normally helps increase the reactivity of startingalpha-olefin polymers with monounsaturated functionalizing reactant, itis not necessary with the unsaturated polymers contemplated for use inembodiments of the invention, particularly those preferred polymerswhich possess a high terminal bond content and reactivity. Preferably,the unsaturated polymer and the monounsaturated functionality reactant,for example, carboxylic reactant, are contacted at elevated temperatureto cause an initial thermal “ene” reaction to take place, thereafter thepartially “ene” reacted polymer is reacted further in the presence of afree-radical initiator.

Thermal “ene” reactions have been heretofore described in U.S. Pat. Nos.3,361,673 and 3,401,118.

In an alternative embodiment, the unsaturated alpha-olefin polymer maybe functionalized, selectively at the sites of olefinically unsaturatedbonds in the polymer chains, with carboxylic acid, carboxylic ester orthiol ester functional groups via a Koch reaction. In accordance withembodiments of the invention, a Koch process comprises contacting apolymer composition comprising at least one polymer having at least onecarbon-carbon double bond, with a Koch catalyst. The catalyst ispreferably a classical Broensted acid or Lewis acid catalyst. Thesecatalysts which are useful for Koch reactions, are distinguishable fromtransition metal catalysts of the type useful in hydroformylationreactions above. The Koch reaction is conducted in a manner and underconditions sufficient to form a carbenium ion at the site of saidcarbon-carbon double bond. The carbenium ion is reacted with carbonmonoxide to form an acylium cation, which in turn is reacted with atleast one nucleophilic trapping agent selected from the group consistingof water or at least one hydroxyl or one thiol group containingcompound. The Koch reaction as applied to polymer in accordance with thepresent invention has resulted in yields of Koch functionalized polymerof at least 40, preferably at least 50, more preferably at least 80, yetmore preferably at least 90 and most preferably at least 95 mole percentof the polymer reacting to form acylium cations which form functionalgroups, for example carbonyl functional groups.

The Koch reaction mechanism permits controlled functionalization ofunsaturated polymers. When carbon of the carbon-carbon double bond issubstitued with hydrogen, it will result in an “iso” functional group orwhen a carbon of the double bond can be fully substituted withhydrocarbyl groups, it will result in an “neo” functional group.

In the Koch process, a polymer having at least one olefinic unsaturationreacted via a Koch mechanism to form the carbonyl or thiol carbonylgroup-containing compounds as well as derivatives thereof. The polymersreact with carbon monoxide in the presence of an acid catalyst or acatalyst complexed with a necleophilic trapping agent. A preferredcatalyst is BF₃ and preferred catalyst complexes include BF₃H₂O and BF₃complexed with 2,4-dichlorophenol. The starting polymer reacts withcarbon monoxide to form a carbenium ion which in turn reacts with thenucleophilic trapping agent, for example water, alcohol (preferably asubstituted phenol) or thiol to form respectively a carboxylic acid,carboxylic ester group, or thiol ester.

Preferred nucleophilic trapping agents are selected from the groupconsisting of water, monohydric alcohols, polyhydric alcoholshydroxyl-containing aromatic compounds and hetero substituted phenoliccompounds. The catalyst and nucleophilic trapping agent can be combinedto form a catalytic complex.

The acid catalyst is preferably selected from the group consisting ofHF, BF₃, BF₃ and H₂SO₄. The catalytic complex can be selected from thegroup consisting of BF₃.xH₂O, BF₃.(2,4-dichlorophenol),BF₃.xH₂O.yn-heptanoic acid, BF₃.yn-heptanoic acid, BF₃.xH₂O.zH₃PO₄, andBF₃.wCH₃SO₃H, wherein x is from 0.5 to 1.5; y is from 0.5 to 2.0, z isfrom 0.5 to 1.5 and w is from 0.5 to 5.0. The acid catalyst or catalystcomplexes preferably have a Hammet acidity value of from −8.0 to −11.5and preferably from −10.0 to −11.5.

Processes for functionalizing unsaturated polymers via a Koch reactionare described more fully in U.S. Pat. No. 5,629,434, entitled“Functionalization of polymers based on Koch chemistry and derivativesthereof.”

In still other preferred embodiments, the unsaturated alpha-olefinpolymers may be functionalized with carboxylic acid or ester moieties byreacting the starting polymers with carbon monoxide and an alcohol inthe presence of a protonic acid and catalyst system comprising (a) atleast one of the metals palladium, rhodium, ruthenium, iridium andcobalt in elemental or compound form and (b) a copper compound.Processes of this type are disclosed, for example, in published EPApplication 148,592.

In preferred embodiments of this invention, the functionalized olefinpolymers are characterized by a high degree of monofunctionality, thatis, at least about 65 and preferably at least about 75 percent of thepolymer chains contain only one functional group (for example, acid oranhydride group) at a point in the respective polymer chains where acarbon-carbon unsaturated bond was located prior to beingfunctionalized.

Some functional groups may be added directly to the interpolymer by, forexample, a Friedel-Crafts reaction or other electrophilic substitutionreaction. Such functional groups include, for example, unsubstituted orsubstituted alkylcarbonyl, arylcarbonyl, and aralkyl groups; carboxylicacid or sulfonic acid groups or alkyl groups substituted with carboxylicacid or sulfonic acid groups; halogen, and NO₂, which can subsequentlybe transformed to NH₂. Preferably such groups include acyl such assubstituted or unsubstituted phenylcarbonyl, carboxyalkylcarbonyl, andsubstituted or unsubstituted carboxybenzyl. Particularly preferredgroups include —C(O)Me which can be further functionalized to, forexample, —CO₂H; —C(O)-pC₆H₄-Me which in turn can be furtherfunctionalized to, for example, —CH(OH)-pC₆H₄-Me; for example,—CH(R⁵)CH₂CH₂CO₂H; —CH(R⁵)CH₂CH₂SO₃H; and —CH(R⁵)-pC₆H₄—CO₂H, wherein R⁵is independantly selected from hydrogen or an alkyl group; and—C(O)CH₂CH₂CO₂H. The functional groups containing acid groups can beconverted to ionomeric salts, such as zinc ionomers by neutralization.The electrophilic substitution reactions which have been discovered tobe advantageously useful for the substantially random polymers describedabove may be conducted as described in G. A. Olah, Friedel-Crafts andRelated Reactions, Vol. II, Part 2, J. Wiley & Sons, N.Y., 1964.

While many of the earlier described substituents may be placed directlyon the interpolymer by an electrophilic substitution reaction, othersubstituents are not amenable to this strategy. For this reason it isoften advantageous to first halomethylate the interpolymer and thentransform the halomethyl group into other substituents by suitablereactions, such as nucleophilic substitution.

Such halomethylation typically employs the dissolution of theinterpolymer in a suitable solvent to perform halomethylation.Generally, a suitable solvent is a compound which will not significantlyreact with any component in the reaction mixture. Preferably, thesolvent is a liquid and remains a liquid at the conditions employed inthe reaction. While different types of solvents may be used, preferredsolvents include, for example, chlorinated hydrocarbons such as1,2-dichloroethane, trichloromethane, methylene chloride, as well as,mixtures thereof. Often, the halomethyl ether reactant itself may beused in excess as a solvent.

Once dissolved, the interpolymer is then reacted with a halomethyl etherhaving the following structure:X—CH₂—O—R⁴wherein X represents a halogen and R⁴ represents an inert group.

X is preferably chloro, bromo, fluoro, or iodo. More preferably X ischloro or bromo. Most preferably X is chloro.

The R⁴ group is not particularly critical so long as the halomethylether is capable of reacting with the interpolymer to form ahalomethylated interpolymer. Thus, R⁴ is an inert group with respect tothe reactants and reaction conditions employed. Typically, R⁴ is a groupselected from substituted or unsubstituted hydrocarbyl. Preferably R⁴ isan alkyl group. More preferably R⁴ is an alkyl group having from one to20 carbon atoms. Most preferably R⁴ is an alkyl group having from one tosix carbon atoms such as, for example, methyl or ethyl.

The specific halomethyl ether which is employed in the halomethylationreaction is generally selected based upon the halomethylatedinterpolymer which is desired. For example, if a chloromethylatedinterpolymer is desired then a chloromethyl ether is employed.Similarly, if a bromomethylated interpolymer is desired then abromomethyl ether is employed.

Preferred halomethyl ethers include halomethyl alkyl ethers such aschloromethyl alkyl ethers and bromomethyl alkyl ethers, for example,chloromethyl methyl ether, chloromethyl ethyl ether, bromomethyl methylether, bromomethyl ethyl ether.

The halomethyl ether is preferably mixed with the dissolvedinterpolymer. However, as one skilled in the art will appreciate, thehalomethyl ether may also first be dissolved in a suitable solvent andthen the interpolymer may be dissolved in the same or a differentsolvent. Additionally, the halomethyl ether may be formed in situ.

The amount of halomethyl ether employed varies depending upon suchfactors as the type of interpolymer, the desired degree ofhalomethylation and the reaction conditions employed. Typically, thehigher the desired degree of halomethylation then the more halomethylether which is required.

The degree of halomethylation may be defined as the mole percent ofhalomethylation per mole of polymer repeat unit containing an aromaticgroup. In the case of ethylene-styrene interpolymer for example, thedegree of halomethylation is the mole percent of phenyl rings which havea halomethyl group attached. For ethylene-styrene interpolymers the molepercent may be from at least 1, preferably at least 5 to 80 percent oreven as much as 100 or 200 percent. As one skilled in the art willappreciate if the degree of halomethylation is above 100 percent thensome aromatic groups will have more than one halomethyl groupsubstitutuent.

Generally, the para position of the phenyl ring is most active and themeta position is the least active. Thus, halomethyl substitution firstoccurs predominantly at the para position of the ethylene-styreneinterpolymer and then at the ortho position. Both the degree ofhalomethylation and the position of substitution may be readilydetermined by NMR spectroscopy.

The interpolymer is preferably reacted with the halomethyl ether in thepresence of a catalytic amount of a suitable catalyst. A suitablecatalyst is a compound which is effective in catalyzingchloromethylation as described in, for example, G. A. Olah,Friedel-Crafts and Related Reactions, Vol. II, Part 2, p. 659, J. Wiley& Sons, N.Y., 1964. Preferably, such catalysts include mild Lewis acidcatalysts such as tin tetrachloride, zinc chloride, and titaniumtetrachloride.

The specific catalyst employed is not critical so long as the catalysthas the appropriate activity. As one skilled in the art will appreciate,the higher the desired degree of halomethylation then the more active acatalyst which may be necessary. In some circumstances the catalyst maybe so active that crosslinking and/or gellation of the interpolymer mayoccur. If crosslinking is not desired then a moderating agent may beadded in a sufficient amount to weaken the catalyst activity and reducethe crosslinking. Such moderating agents are compounds such as, forexample, ethers. Thus, ethers such as alkyl ethers, aromatic ethers andmixtures thereof will often moderate the catalyst activity. A preferredether which has shown effectiveness as a moderating agent is diethylether.

The amount of catalyst added will vary depending upon such factors asthe particular catalyst employed, the type and amount of interpolymerand halomethyl ether being reacted, as well as, the desired degree ofhalomethylation. In general, however, the molar ratio of halomethylether to catalyst often determines the degree of halomethylation, aswell as, the amount of crosslinking which occurs. Therefore, for mostapplications the molar ratio of halomethyl ether to catalyst is usuallyat least 5, preferably at least 10, more preferably at least 20. On theother hand, the molar ratio of halomethyl ether to catalyst is usuallyno more than 1000, preferably no more than 100, more preferably no morethan 50.

The pressure and temperature of the halomethylation reaction should beregulated such that the reaction proceeds as desired. Typically, thereaction is carried out at ambient pressure. However, other pressuresmay be employed so long as the reaction is not hindered.

Many different temperatures may be employed. Typically, if thetemperature is low then the reaction proceeds slowly. On the other hand,if the temperature is high then the reaction proceeds more quickly andmay even result in crosslinking. In general, temperatures of at least−50° C., preferably at least 0° C., more preferably at least 10° C. maybe employed. Correspondingly, temperatures of less than 100, preferablyless than 50, more preferably less than 30° C. may be employed.

The reaction should be allowed to proceed until the desired degree ofhalomethylation has been reached. As one skilled in the art willappreciate, such times will vary depending upon the desired degree ofhalomethylation, as well as, the particular catalyst employed and thereaction conditions. Typically, higher degrees of halomethylation willrequire a longer reaction time. However, generally reaction times may bereduced by employing more halomethylating agent and/or more activecatalysts and/or higher temperatures. Generally, the reaction time is atleast 0.5, preferably at least 2, more preferably at least 8 hours.Correspondingly, the reaction time is usually less than 72, preferablyless than 48, more preferably less than 24 hours.

The halomethylated interpolymer may be recovered by any suitable means.A particularly advantageous recovery method is to add a quenching amountof water when the desired degree of halomethylation has been reached.The water which is added is preferably at a temperature below that ofthe reaction and above the water's freezing point at the pressureemployed in the reaction.

The actual amount and temperature of the water which is added is notcritical so long as the reaction is quenched and a readily separableaqueous layer and an organic layer are formed. The organic layercomprises halomethylated interpolymer and solvent. The two layers may beseparated and the halomethylated interpolymer may then be isolated fromthe organic layer and dried. While the isolation may be accomplished byany suitable means, a convenient means of isolation is precipitation.

The properties of the halomethylated resins usually differ widelydepending upon the type of halogen, the type of interpolymer, and theextent of halomethylation. Generally, chloromethylation appears to havelittle effect on the glass transition temperature and the thermalstability of ethylene-styrene interpolymer. For example, the glasstransition temperature of ethylene styrene copolymer containing 70weight percent styrene increases from 26.5° C. to 29° C. when 44 molepercent of the phenyl groups are chloromethylated and the thermalstability appears comparable to that of the parent interpolymer.

Once the interpolymer has been halomethylated, the halomethyl groups maybe transformed to other functional groups if desired. The transformationmay occur in solution or in an interpolymer melt in, for example, anextruder. Numerous transformations are possible. For example, thehalomethyl group can be used for simple crosslinking (by reaction with aLewis acid, a dinucleophile or water or induced by radiation), reactivecompatibilization with other polymers, or for introduction of a plethoraof other functional groups onto the polymer backbone. Functional groupsto which the halomethyl group can be transformed include, for example,phosphonium, ammonium, sulfonium, ester, hydroxyl, ether, amine,phosphine, thiol, cyano, carboxylic acid, amide, or a functional groupderived from reaction with nucleophiles, and mixtures thereof within theinterpolymer. Such functionalization from halomethyl groups has beendescribed in, for example, U.S. Pat. No. 5,162,445; P. Hodge, “Polymersas Chemical Reagents”, Encyclopedia of Polymer Science and Engineering2nd Edition, pp. 618-658; and Monthead et al., “Chemical Transformationsof Chloromethylated Polystyrene,” IMS-Review Macromolecular ChemicalPhysics, 1988, pp. 503-592. Suitable such methods may be used to formthe transformed interpolymers.

Testing Methods

Unless indicated otherwise, the following testing procedures are to beemployed: Density is measured in accordance with ASTM D-792. The samplesare annealed at ambient conditions for 24 hours before the measurementis taken.

Melt index (I₂), is measured in accordance with ASTM D-1238, condition190° C./2.16 kg (formally known as “Condition (E)”). It should beunderstood that for some low molecular weight polymers their melt indexcould not be measured by this method due to the low molecular weight.

Molecular weight is determined using gel permeation chromatography (GPC)on a Waters 150° C. high temperature chromatographic unit equipped withthree mixed porosity columns (Polymer Laboratories 103, 104, 105, and106), operating at a system temperature of 140° C. The solvent is1,2,4-trichlorobenzene, from which 0.3 percent by weight solutions ofthe samples are prepared for injection. The flow rate is 1.0 mL/min. andthe injection size is 100 microliters.

The molecular weight determination is deduced by using narrow molecularweight distribution polystyrene standards (from Polymer Laboratories) inconjunction with their elution volumes. The equivalent polyethylenemolecular weights are determined by using appropriate Mark-Houwinkcoefficients for polyethylene and polystyrene (as described by Williamsand Word in Journal of Polymer Science, Polymer Letters, Vol. 6, (621)1968, to derive the following equation:M _(polyethylene) =a*(M _(polystyrene))^(b)

In this equation, a=0.4316 and b=1.0. Weight average molecular weight,M_(w), is calculated in the usual manner according to the followingformula: M_(w)=Σw_(i)*M_(i), where w_(i) and M_(i) are the weightfraction and molecular weight, respectively, of the ith fraction elutingfrom the GPC column.

Melt viscosity is determined in accordance with the following procedureusing a Brookfield Laboratories DVII+Viscometer in disposable aluminumsample chambers. The spindle used is a suitable spindle (for example, aSC-31 hot-melt spindle), for measuring viscosities in the range of from10 to 100,000 centipoise. A cutting blade is employed to cut samplesinto pieces small enough to fit into the 1 inch wide, 5 inches longsample chamber. The sample is placed in the chamber, which is in turninserted into a Brookfield Thermosel and locked into place with bentneedle-nose pliers. The sample chamber has a notch on the bottom thatfits the bottom of the Brookfield Thermosel to ensure that the chamberis not allowed to turn when the spindle is inserted and spinning. Thesample is heated to about 300° F., with additional sample being addeduntil the melted sample is about 1 inch below the top of the samplechamber. The viscometer apparatus is lowered and the spindle submergedinto the sample chamber. Lowering is continued until brackets on theviscometer align on the Thermosel. The viscometer is turned on, and setto a shear rate which leads to a torque reading in the range of 30 to 60percent. Readings are taken every minute for about 15 minutes, or untilthe values stabilize, which final reading is recorded.

Percent crystallinity is determined by differential scanning calorimetryusing a Perkin-Elmer DSC 7. The percent crystallinity may be calculatedwith the equation:percent C=(A/292 J/g)×100,wherein percent C represents the percent crystallinity and A representsthe heat of fusion of the ethylene in Joules per gram (J/g).

EXAMPLES

General: All organometallic reactions and polymerizations were performedunder a purified argon or nitrogen atmosphere in a Vacuum Atmospheresglove box, using glassware previously dried in a vacuum oven at 150° C.overnight. All solvents used were an hydrous, dc-oxygenated and purifiedaccording to known techniques. All ligands and metal precursors wereprepared according to procedures known to thus of skill in the art, forexample, under inert atmosphere conditions, etc. Ethylene/styrenecopolymerizations were carried out in a parallel pressure reactor, whichis fully described in WO 00/09255, and U.S. Pat. No. 6,306,658.

High temperature Size Exclusion Chromatography (also known as gelpermeation chromatography, “GPC”) was performed using an automated“Rapid GPC” system as described in U.S. Pat. Nos. 6,175,409, 6,260,407,and 6,294,318. A series of two 30 cm×7.5 mm linear columns were used,with one column containing PLgel 10 um, MixB and the other columncontaining PLgel 5 um, MixC (available from Polymer Labs). The GPCsystem was calibrated using narrow polystyrene standards. The system wasoperated at a eluent flow rate of 1.5 mL/min and an oven temperature of160° C. o-dichlorobenzene was used as the eluent. The polymer sampleswere dissolved 1,2,4-trichlorobenzene at a concentration of about 1mg/mL. Between 40 μL and 200 μL of a polymer solution were injected intothe system. The concentration of the polymer in the eluent was monitoredusing an evaporative light scattering detector. All of the molecularweight results obtained are relative to linear polystyrene standards.

Due to the low molecular weight of the ethylene-styrene copolymersproduced by the catalyst systems described herein, the resolutionobtainable using the Rapid GPC system is limited by the lower exclusionlimit of the column material. Because the molecular weights of theproducts made in some embodiments of the invention are close to or belowthe lower size exclusion limit of the GPC columns, the M_(w) (weightaverage molecular weight) and especially the M_(n) (number averagemolecular weight) obtained by GPC are overestimated, while thepolydispersity index (PDI=M_(w)/M_(n)) is underestimated, due to thelowest molecular weight fractions, which are below the size exclusionlimit of the column material, eluting at approximately the same time asthe higher molecular weight fractions which are at or slightly above thelower exclusion limit. The M_(w) and PDI shown in Table 4b illustratethis dependence of measured PDI on molecular weight. However, in someembodiments, this may not be the case.

The ratio of styrene to ethylene incorporated in the polymer products,represented as the mol percent of styrene incorporated in the polymer(mol percent incorporated styrene) was determined using ¹H NMRspectroscopy (described below). The total styrene content of the polymerproducts (mol percent total styrene), including both the styreneincorporated in the ethylene-styrene copolymer and any backgroundhomopolystyrene (PS) in the product sample, was determined using FTIRspectroscopy (linear regression method, described below).

¹H NMR method for determining mol percent styrene incorporation: Theratio of styrene to ethylene incorporated in the polymer products,represented as the mol percent (mole percent) of styrene incorporated inthe polymer was determined using ¹H NMR spectroscopy. NMR samples wereprepared as a solution of 10-40 mg of polymer in 0.4-0.5 mL of a 50/50mixture by volume of 1,1,2,2-tetrachloroethane-d2 (TCE-d2) andtetrachloroethylene (Perchlor). Depending on the specific polymer, thesample was heated to completely dissolve the polymer. NMR was taken at atemperature between 20 and 90° C., such that the sample was fullydissolved. Proton NMR spectra of samples were acquired on a Bruker 300MHz NMR spectrometer. Abbreviations used below: iS=incorporated styrene(styrene incorporated into ethylene-styrene copolymer), aPS=atactichomopolystyrene, S=total styrene=iS+aPS, E=ethylene.

Data Analysis

The ¹H NMR spectra are integrated using the following regions:

Styrene Aromatic = 7.687–6.869 ppm = region A Atactic PolystyreneAromatic = 6.869–6.357 ppm = region B Vinyl Region = 5.95–4.7 ppm =region D CH and CH₂ Aliphatic = 3.212–1.0 ppm = region E Methyl =1.0–0.50 ppm = region F region C = D + E + FCalculations:Moles Styrene=N(S)=(styrene region A+aPS region B)/5Moles aPS=N(aPS)=(aPS region B)/2Moles Ethylene=N(E)=(region C−N(S)*3)/4N(iS)/N(E)=N(S)−N(aPS)/N(E)wt. percent E=N(E)*28/(N(E)*28+N(S)*104)wt. percent S (total)=N(S)*104/(N(E)*28+N(S)*104)wt. percent aPS=N(APS)*104/(N(E)*28+N(S)*104)wt. percent iS=(N(S)−N(aPS))*104/(N(E)*28+N(S)*104)molpercent iS=(N(iS)/N(E))*100/(1+(N(iS)/N(E))N(vinyl)=region D/3Chain length=(N(E)+N(iS))/N(vinyl)iS units per chain=(N(S)−N(aPS))/N(vinyl)E units per chain=N(E)/N(vinyl)Average molecular weight (Mn)=iS units per chain*104+E units perchain*28

FTIR method for determining mol percent total styrene in product: FTIRwas performed on a Bruker Equinox 55+IR Scope II in reflection modeusing a Pike MappIR accessory with 16 scans. The ratio of total styreneto ethylene was obtained from the ratio of band heights at 4330 cm⁻¹ and1602 cm⁻¹. This method was calibrated using a set of ethylene-styrenecopolymers with a range of known styrene content.

The total styrene content of the polymer products (mol percent totalstyrene), includes both the styrene incorporated in the ethylene-styrenecopolymer and any background homopolystyrene (PS) in the product sample.For the ethylene-styrene copolymerization conditions employed inExamples 3 and 4, the homopolystyrene background level is less than 3.5wt percent (1 mol percent) and decreases (in percentage terms) withincreasing product yield. For the products made in some embodiments ofthe invention that were analyzed by ¹H NMR, the homopolystyrene contentwas always below 3.5 weight percent (for Example 3.6, product yield=82mg) and more typically below 2 weight percent for product yields or 100mg or more.

Ligand Examples

The following ligands are used in some of these examples:

Ligand Synthesis Examples. General

¹H NMR spectra were recorded on ligand solution in CDCl₃ and arereported relative to residual chloroform or TMS as the internalstandard. Mass spectra were obtained by EI at 70 eV. Chromatographyrefers to flash chromatography on silica gel (230-400 mesh). Allsolvents used were anhydrous, and purified according to knowntechniques. All chemicals were purchased by Aldrich except for4-tert.-butyl-2-phenylphenol (Avocado), xantphos and2-(di-t-butylphosphino)biphenyl (Strem), and benzene boronic acid(Lancaster).

Example 1 Synthesis of Ligands

This example describes a general synthesis route that was used for thevariety of ligands used herein, with the starting materials changed asappropriate.

To a suspension of 4-chloro-2-nitroaniline (269 mg, 1.6 mmol) in HCl (37percent, 4 mL) is added H₂O (1 mL) and NaNO₂ (720 μL of a 2.5 M solutionin H₂O, 1.6 mmol) at 0° C. After stirring at room temperature for 10minutes the resulting solution is added drop-wise to a solution of4-tert-butyl-2-phenylphenol (362 mg, 1.6 mmol) and NaOH (2 g, 50 mmol)in H₂O (10 mL) and MeOH (10 mL) at 0° C. A precipitate forms which,after the addition is complete, is filtered, dissolved in ethyl acetate,washed with H₂O and brine, and dried over Na₂SO₄. After removal of thesolvent, the solid is suspended in a mixture of EtOH (10 mL) and aqueousNaOH (7 mL of a 2 M solution in H₂O, 14 mmol). Zn (700 mg, 10.8 mmol) isadded and the resulting mixture is stirred for 30 min at 90° C. Afterfiltration, a solution of NH₄Cl in H₂O is added, the mixture isextracted with ethyl acetate, and the combined organic layers are washedwith brine and dried over Na₂SO₄. Purification by column chromatographyover silica gel using hexanes/methylene chloride (10/1) as eluent gives145 mg (0.385 mmol, 24 percent) of the desired product as a yellowsolid. ¹H NMR (CDCl₃, 400 MHz): δ 11.38 (s, 1H), 8.39 (d, J=2.5 Hz, 1H),7.92 (d, J=1.5 Hz, 1H), 7.87 (d, J=7 Hz, 1H), 7.64 (dd, J=1.5 Hz/7 Hz,2H), 7.50-7.35 (m, 5H), 1.41 (s, 9H). One peak in GC-MS, m/z 377.

Ligands B, C, D, E, H and J were prepared following the syntheticmethodology used for Ligand A. Ligand F was purchased from Aldrich (CASregistry # 3864-99-1), and Ligand G were purchased from Lancaster (CASregistry # 3864-71-7).

Synthesis of Phenols with Aryl Substitution at the 2-Position:

Following Scheme 2, to a solution on 2-bromo-4-methylanisole (10 g, 49.7mmol) in anhydrous THF (50 mL) is added n-butyllithium (32.6 mL of a 1.6M solution in hexanes, 52.2 mmol) at −78° C. After stirring at −78° C.for 10 minutes and at room temperature for 1 hour, the solution iscooled again to −78° C. and triisopropyl borate (12.6 mL, 52.2 mmol) isadded slowly. After the solution is stirred at room temperature for 1hour, a solution of NH₄Cl in H₂O is added. The mixture is extracted withether, and the combined organic layers are washed with brine and driedover Na₂SO₄. The crude product is recrystallized from ether to give the5.6 g of the boronic acid (33.7 mmol, 68 percent) as a white solid.

Under an atmosphere of argon, Na₂CO₃ (10 mL of a 2 M solution in H₂O, 20mmol) is added to a solution of the boronic acid (3.73 g, 22.5 mmol),1-bromonaphthalene (5 g, 20 mmol), and Pd(PPh₃)₄ (462 mg, 0.4 mmol) inDME (40 mL). After stirring for 12 hours at 80° C., H₂O is added and theresulting mixture is extracted with ether. The combined organic layersare washed with brine and dried over Na₂SO₄. After removal of thesolvent, 5 g of the crude product is obtained.

The crude product is then dissolved in anhydrous methylene chloride (30mL), and to this solution is then added a solution of BBr₃ (24 mL of a 1M solution in methylene chloride, 24 mmol). After the solution isstirred at room temperature for 1 hour, brine is added. The mixture isextracted with methylene chloride, and the combined organic layers arewashed with brine and dried over Na₂SO₄. Purification by columnchromatography over silica gel using hexanes/ethyl acetate (10/1) aseluent gives 3.3 g (14.1 mmol, 71 percent) of the desired product as ayellow solid. ¹H NMR (CDCl₃, 400 MHz): δ 7.95 (d, J=8 Hz, 2H), 7.71 (d,J=8 Hz, 1H), 7.62-7.45 (m, 4H), 7.21 (d, J=8 Hz, 1H), 7.11 (s, 1H), 6.98(d, J=8 Hz, 1H), 2.39 (s, 3H). ¹³C NMR (CDCl₃, 100 MHz): δ 150.9, 134.2,133.9, 131.8, 131.5, 130.0, 129.7, 128.7, 128.4 (2×), 128.1, 126.7,126.3, 126.0, 125.7, 115.3, 20.5. One peak in GC-MS, m/z 234.

Synthesis of Phenols with Variation in the 2- and 4-Position:

Following Scheme 3, a mixture of 4-bromo-2-chlorophenol (4.66 g, 22.45mmol), iodomethane (3.1 mL, 50 mmol), and powdered K₂CO₃ (13.8 g, 100mmol) in acetone (20 mL) is stirred at 65° C. for 1 hour. Afterfiltration and removal of the solvent, 4.3 g (19.4 mmol, 86 percent) of4-bromo-2-chloroanisole are obtained as a white solid.

The 4-bromo-2-chloroanisole (1 g, 4.52 mmol), plus2,6-dimethylbenzenethiol (640 μL, 4.8 mmol) and NaOtBu (770 mg, 8 mmol)are then added to a solution of Pd(dba)₂ (60 mgs, 0.1 mmol) and xantphos(120 mg, 0.2 mmol) in toluene (10 mL). After stirring the resultingmixture at 110° C. for 3 h, a solution of NH₄Cl in H₂O is added, themixture is extracted with hexanes, and the combined organic layers arewashed with brine and dried over Na₂SO₄. Purification by columnchromatography over silica gel using hexanes/ethyl acetate (10/1) aseluent gives 1.15 g (4.14 mmol, 92 percent) of the desired anisolethioether as a yellow oil. To a solution of Pd(OAc)₂ (11 mg, 0.05 mmol)and 2-(di-t-butylphosphino)biphenyl (30 mg, 0.1 mmol) in THF (3 mL) isadded the anisole thioether (278 mg, 1 mmol), benzene boronic acid (183mg, 1.5 mmol) and CsF (456 mgs, 3 mmol). The resulting mixture isstirred at room temperature for 16 h, at 60° C. for 4 hours, and thenfiltered. Purification by column chromatography over silica gel usinghexanes/ethyl acetate (20/1) as eluent gives 293 mg (0.92 mmol, 92percent) of the desired 2-phenyl-substituted anisole thioether as ayellow solid (the crude product).

To a solution of the crude product in anhydrous methylene chloride (5mL) is added BBr₃ (1.5 mL of a 1 M solution in methylene chloride, 1.5mmol). After the solution is stirred at room temperature for 30 minutes,brine is added. The mixture is extracted with methylene chloride, andthe combined organic layers are washed with brine and dried over Na₂SO₄.Purification by column chromatography over silica gel usinghexanes/ethyl acetate (20/1) as eluent gives 143 mg (0.47 mmol, 47percent) of the desired product as a yellow solid. ¹H NMR (CDCl₃, 400MHz): δ 7.53-7.37 (3, 6H), 7.25-7.12 (m, 2H), 6.97 (dd, J=1.3 Hz/1.3 Hz,1H), 6.83 (dd, J=1.3 Hz/1.3 Hz, 2H), 5.12 (s, 1H), 2.48 (s, 6H). Onepeak in GC-MS, m/z 306.

Example 2 Synthesis of Metal-Ligand Complexes

The following complexes are prepared herein (Bz=benzyl=CH₂Ph):

-   Complex 1. Ligand A (630 mg, 1.67 mmol) was dissolved in C₆D₆ (3    mL). Solid Zr(CH₂Ph)₄ (380 mg, 0.84 mmol) was added and the mixture    was heated to 60° C. for 1 hour. The solvent was removed, and the    resulting red-orange solid was extracted into boiling pentane (15    mL) and filtered. The volume of the filtrate was reduced to 5 mL and    the filtrate was cooled to −35° C. overnight. An orange precipitate    was collected, washed with cold pentane and dried in vacuo (565 mg,    65 percent yield). ¹H NMR (C₆D₆, 25 C): δ 8.50 (s, 2H, OAr), 7.94    (d, 4H, benzotriazole Ar), 7.69 (s, 2H, OAr or benzoltriazole Ar),    7.45 (s, 2H, OAr or benzoltriazole Ar), 7.1-7.5 (overlapping m, 10H,    CH₂Ph), 6.2-6.7 (m, 10H, Ph), 2.4 (dd, Zr(CH₂Ph), 1.28 (s, 18H,    tBu).-   Complex 2: In a manner similar to that described for Complex 1,    Complex 2 was prepared from ligand B (77 mg, 0.19 mmol) and    Zr(CH₂Ph)₄ (46 mg, 0.10 mmol). ¹H NMR data was consistent with the    proposed formula.-   Complex 3: In a manner similar to that described for Complex 1,    Complex 3 was prepared from ligand C (88 mg, 0.20 mmol) and    Zr(CH₂Ph)₄ (46 mg, 0.10 mmol). ¹H NMR data was consistent with the    proposed formula.-   Complex 4: In a manner similar to that described for Complex 1,    Complex 4 was prepared from ligand D (71 mg, 0.21 mmol) and    Zr(CH₂Ph)₄ (48 mg, 0.11 mmol). ¹H NMR data was consistent with the    proposed formula.-   Complex 5: In a manner similar to that described for Complex 1,    Complex 5 was prepared from ligand E (75 mg, 0.23 mmol) and    Zr(CH₂Ph)₄ (58 mg, 0.13 mmol). ¹H NMR data was consistent with the    proposed formula.-   Complex 6: In a manner similar to that described for Complex 1,    Complex 6 was prepared from ligand F (371 mg, 1.04 mmol) and    Zr(CH₂Ph)₄ (225 mg, 0.50 mmol). ¹H NMR data was consistent with the    proposed formula.

Examples 3-4 Ethylene-Styrene Copolymerization Experiments

The polymerization reactions were carried out in a parallel pressurereactor (which is described in the patent and patent applications citedabove) located within an inert atmosphere drybox. The premixing of themetal-ligand complex or composition with alkyl (group 13 reagent) andactivator solutions was performed in an array of 1 mL vials locatedadjacent to the parallel pressure reactor in the inert atmospheredrybox. A liquid dispensing robot was used to add/remove liquids to/fromthe 1 mL vials and to inject solutions and liquid reagents into theparallel pressure reactor.

Preparation of the polymerization reactor prior to injection of catalystcomposition: A pre-weighed glass vial insert and disposable stirringpaddle were fitted to each reaction vessel of the reactor. The reactorwas then closed, 0.10 mL of a 0.02 M solution in toluene of the samegroup 13 reagent used as the “premix alkyl” for each example, followedby 3.8 mL of toluene, were injected into each pressure reaction vesselthrough a valve. The temperature was then set to 110° C., and thestirring speed was set to 800 rpm, and the mixture was exposed toethylene at 100 psi pressure. A ethylene pressure of 100 psi in thepressure cell and the temperature setting were maintained, usingcomputer control, until the end of the polymerization experiment.

Preparation of the premix alkyl and activator stock solutions: Theactivator solution is a 2.5 mM solution of [PhNMe₂H]⁺[B(C₆F₅)₄]⁻(N,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate, “ABF20”) intoluene heated to approximately 85° C. to dissolve the reagent, or a 2.5mM toluene solution of [PhN((CH₂)_(n″)CH₃)₂H]⁺[B(C₆F₅)₄]⁻ 0 (where n″ is14, 16 or 18, shown in table 2a as [PhNR₂H]⁺[B(C₆F₅)₄]⁻) or a 7.5 mMtoluene solution of B(C₆F₅)₃. The premix alkyl (“group 13 reagent”)solution is either a 0.050 M solution of Akzo-Nobelpolymethylaluminoxane-improved process (PMAO-IP) or a 0.050 M solutionof Akzo-Nobel modified methylaluminoxane-3A (MMAO), or a 0.20 M solutionof diisobutyl aluminum hydride (DIBAL-H). All “group 13 reagent”solutions were solutions in toluene. See also WO 02/02577 for activatorsynthesis for examples 3.7, 3.8, 3.9 and 3.11.

Polymerization: After injection of solutions into the pressure reactorvessel (described below) the polymerization reactions were allowed tocontinue at 110° C. polymerization temperature for the time shown intables 1b, 2b, 3b and 4b (shown for each example as “Run time”), duringwhich time the temperature and pressure were maintained at their pre-setlevels by computer control. The polymerization times were the lesser ofthe maximum desired polymerization reaction time or the time taken for apredetermined amount of ethylene gas to be consumed in thepolymerization reaction. After the reaction time elapsed, the reactionwas quenched by addition of an overpressure of carbon dioxide sent tothe reactor.

Product work-up: After the polymerization reaction, the glass vialinsert, containing the polymer product and solvent, was removed from thepressure cell and removed from the inert atmosphere dry box, and thevolatile components were removed using a centrifuge vacuum evaporator.After most of the volatile components had evaporated, the vial contentswere dried thoroughly in a vacuum oven at 75° C. The vial was thenweighed to determine the yield of polymer product. The polymer productwas then analyzed by rapid GPC, as described above to determine themolecular weight of the polymer produced, and by FTIR spectroscopy todetermine the styrene content. Selected samples were additionallyanalyzed using ¹H NMR spectroscopy for styrene incorporation and vinylend group content.

Example 3 Ethylene-Styrene Copolymerization Using Metal-Ligand Complexes

12 polymerization reactions were carried out with different metal-ligandcomplexes for the copolymerization of ethylene and styrene. For thefollowing descriptions, the volumes of the reagent solutions added tothe 1 mL vial and to the pre-pressurized polymerization reaction vesselare shown in Tables 1a and 2a. Polymerization results and product dataare shown in Tables 1b and 2b.

Injection of solutions into the pressure reactor vessel (after“preparation of the polymerization reactor” and immediately prior to“polymerization”) for Example 3.1-3.12.: First, the appropriate amount(“premix alkyl volume”) of the 0.050 M group 13 reagent solution (forexample 0.040 mL of 0.050 M solution of PMAO-IP for Example 3.1) wasdispensed into a 1 mL vial. Then the appropriate amount of the toluenesolution of the metal-ligand complex (“complex volume”) was added to the1 mL vial (for example 0.080 mL of a 5 mM solution (0.40 μmol) ofComplex 1 for Example 3.1). This mixture was held at room temperaturefor 1 minute, during which time 0.420 mL of styrene followed immediatelyby 0.380 mL of toluene were injected into the pre-pressurized reactionvessel. Then, an appropriate amount (“activator volume”) of theactivator solution (for example 0.176 mL of a 2.5 mM toluene solution(0.44 μmol) of N,N′-dimethylanilinium tetrakis(pentafluorophenyl)borate(“ABF20”) for Example 3.1) was added to the 1 mL vial. For Example 3.6,0.40 mL of toluene was added to the 1 mL vial prior to addition of theother reagents, bringing the total volume of the 1 mL via contents to0.724 mL after addition of the premix alkyl, complex and activatorsolutions. For Example 3.12, 0.185 mL of toluene was added to the 1 mLvial prior to addition of the other reagents, bringing the total volumeof the 1 mL via contents to 0.370 mL after addition of the premix alkyl,complex and activator solutions. After 30 seconds, an appropriate volume(the “injection volume”, calculated as the total volume of the 1 mL vialcontents multiplied by the “injection fraction”) was aspirated from the1 mL vial and injected into the pre-pressurized reaction vessel (forexample for Example 3.1 this corresponds to a total volume of 0.296 mLmultiplied an “injection fraction” of 0.25, providing an injectionvolume of 0.074 mL, corresponding 0.10 μmol of the complex), followedimmediately by approximately 0.7 mL of toluene injected into thepre-pressurized polymerization reaction vessel, to bring the totalsolution volume in the pressurized reaction vessel to 5.5 mL. Thepolymerization and product work-up were then performed as describedabove.

Example 4 Preparation of Ligand/Metal Compositions and Ethylene/StyreneCopolymerizations Using Ligand/Metal Compositions

For the following descriptions, the volumes of the reagent solutionsadded to the 1 mL vial and to the pre-pressurized polymerizationreaction vessel are shown in Tables 3a and 4a. Polymerization resultsand product data are shown in Tables 3b and 4b.

In situ preparation of metal-ligand compositions: Stock solutions wereprepared as follows: The “metal precursor solution” is a 10 mM solutionof Zr(CH₂Ph)₄ or Hf(CH₂Ph)₄ or Zr(NMe₂)₄ or Hf(NMe₂)₄ in toluene. The“ligand solutions” are 25 mM solutions of the representative ligands intoluene, (0.80 μmol), prepared in an array of 1 mL glass vials bydispensing 0.032 mL of a 25 mM ligand solution (0.80 μmol) in a 1 mLglass vial. To each 1 mL glass vial containing ligand/toluene solutionwas added 0.040 mL of the metal precursor solution (0.40 μmol), to formthe metal-ligand combination solution.

For Examples 4.1-4.4 and 4.6-4.9 the reaction mixtures we heated to 70°C. for 1 hour, after which time the products were cooled to ambienttemperature. Prior to addition of alkylation and activator solution, thevolume of the metal-ligand combination solution (which was reduced dueto solvent evaporation) was measured, and this “initial solvent volume”was used in subsequent calculations of vial contents total volume andthe “injection volume”. For Examples 4.3 and 4.4 an additional 0.10 mLof toluene was added to the 1 mL vial at this stage.

For Examples 4.5 and 4.10 the reaction mixtures were heated to 80° C.for 1.5 hours, after which time the products were cooled to ambienttemperature. The reaction mixtures were then dried completely by blowinga stream of argon over the 1 ml vial. Prior to addition of the premixalkyl (group 13 reagent) solution and activator solution, a volume oftoluene (shown in table 3a as “initial solvent volume”) was added to 1mL vial containing the metal-ligand combination solution. This “initialsolvent volume” was used in subsequent calculations of vial contentstotal volume and the “injection volume”.

Injection of solutions into the pressure reactor vessel (after“preparation of the polymerization reactor” and immediately prior to“polymerization”) for Examples 4.1-4.10: To the ligand-metalcomposition, a volume (shown in Table 3a or 4a for each example) of a500 mM solution of 1-octene in toluene was added. Then, an appropriateamount of the group 13-reagent solution (shown in Table 3a or 4a foreach example) was added to the 1 mL vial. This mixture was held at roomtemperature either for 1 minute for Examples 4.1-4.4 and 4.6-4.9, or for10 minutes for Examples 4.5 and 4.10, during which time 0.420 mL ofstyrene followed immediately by 0.380 mL of toluene, were injected intothe pre-pressurized reaction vessel. Then, an appropriate amount of the“activator solution” (shown in Table 3a or 4a for each example) wasadded to the 1 mL vial. After a wait time of 30 seconds, a fraction (the“injection fraction” shown in Table 3a or 4a) of the total volume of the1 mL vial contents (the “injection volume”) was injected into thepre-pressurized reaction vessel, followed immediately by approximately0.7 mL of toluene, to bring the total solution volume in the pressurizedreaction vessel to 5.5 mL. The polymerization and product work-up werethen performed as described above.

TABLE 1a Ethylene-Styrene Copolymerization Experiments using isolatedcomplexes: Solution Premix and Injection Details Example # 3.1 3.2 3.33.4 3.5 3.6 Complex # 1 3 3 2 2 6 Complex solution 0.005 0.005 0.0050.005 0.005 0.004 concentration (M) Complex Volume (mL) 0.080 0.0800.080 0.080 0.080 0.100 μmol of complex added to 0.40 0.40 0.40 0.400.40 0.40 1 mL vial Premix Alkyl PMAO-IP PMAO-IP PMAO-IP PMAO-IP MMAOPMAO-IP (group 13 reagent) Premix Alkyl Volume (mL) 0.040 0.040 0.0400.040 0.040 0.048 Premix Alkyl/Zr ratio 5/1 5/1 5/1 5/1 5/1 6/1Activator ABF20 ABF20 ABF20 ABF20 ABF20 ABF20 Activator Volume (mL)0.176 0.176 0.176 0.176 0.176 0.176 Activator/Zr ratio 1.1/1 1.1/1 1.1/11.1/1 1.1/1 1.1/1 Injection Fraction 0.25 0.25 0.125 0.125 0.125 0.0075Injection Volume (mL) 0.074 0.074 0.037 0.037 0.037 0.005 μmol Zrinjected into reactor 0.10 0.10 0.05 0.05 0.05 0.003

TABLE 1b Ethylene-Styrene Copolymerization Experiments using isolatedcomplexes: Polymerization Details and Results Example # 3.1 3.2 3.3 3.43.5 3.6 Complex # 1 3 3 2 2 6 μmol Zr injected into reactor 0.10 0.100.05 0.05 0.05 0.003 Run Time (Minutes) 10.7 3.1 5.5 9.2 4.1 10.0Polymer Yield (mg) 202 148 124 140 166 82 Activity (mg polymer per μmolper minute) 188 479 454 305 815 2717 mol percent incorporated Styrene by¹H NMR 11.1 10.0 9.4 9.8 11.1 4.9 Average # Styrene units per chain (by¹H NMR) 2.5 1.3 1.2 1.3 1.5 1.3 Average # Ethylene units per chain (by¹H NMR) 20 12 12 12 12 25 Average # monomer units per chain (by ¹H NMR)22 13 13 13 13 27 Mn by ¹H NMR 810 460 450 460 480 840 Ratio ofmethyl/vinyl region integrations (¹H NMR) 1.0 0.9 0.8 0.9 0.9 1.1 molpercent total styrene by FTIR (linear regression) 12.9 12.3 11.2 12.313.1 6.2 Mw × 10⁻³ (by GPC) 3.4 2.4 2.5 3.0 3.0 2.2 Mw/Mn (by GPC) 1.51.4 1.4 1.4 1.5 1.3

TABLE 2a Ethylene-Styrene Copolymerization Experiments using isolatedcomplexes: Solution Premix and Injection Details Example # 3.7 3.8 3.93.10 3.11 3.12 Complex # 1 3 2 1 4 5 Complex solution 0.005 0.005 0.0050.005 0.005 0.004 concentration (M) Complex Volume (mL) 0.080 0.0800.080 0.050 0.050 0.050 μmol of complex added 0.40 0.40 0.40 0.25 0.250.20 to 1 mL vial Premix Alkyl PMAO-IP PMAO-IP MMAO MMAO MMAO MMAO(group 13 reagent) Premix Alkyl 0.040 0.040 0.040 0.025 0.025 0.025Volume (mL) Premix Alkyl/Zr ratio 5/1 5/1 5/1 5/1 5/1 5/1 Activator[PhNR₂H]⁺ [PhNR₂H]⁺ [PhNR₂H]⁺ B(C₆F₅)₃ [PhNR₂H]⁺ B(C₆F₅)₃ [B(C₆F₅)₄]⁻[B(C₆F₅)₄]⁻ [B(C₆F₅)₄]⁻ [B(C₆F₅)₄]⁻ Activator Volume (mL) 0.176 0.1760.176 0.110 0.110 0.110 Activator/Zr ratio 1.1/1 1.1/1 1.1/1 3.3/1 1.1/13.3/1 Injection Fraction 0.125 0.125 0.125 0.40 0.40 0.063 InjectionVolume (mL) 0.037 0.037 0.037 0.074 0.074 0.023 μmol Zr injected 0.0500.050 0.050 0.10 0.10 0.013 into reactor

TABLE 2b Ethylene-Styrene Copolymerization Experiments using isolatedcomplexes. Example # 3.7 3.8 3.9 3.10 3.11 3.12 Complex # 1 3 2 1 4 5μmol Zr injected 0.050 0.050 0.050 0.10 0.10 0.013 into reactor Run Time(Minutes) 5.6 6.1 2.7 5.0 3.9 5.7 Polymer Yield (mg) 225 122 193 219 232154 Activity (mg polymer per 797 396 1428 438 589 2140 μmol Zr perminute) Mol percent total styrene 14.0 11.4 14.0 13.4 14.8 4.8 by FTIR(linear regression) Mw by GPC 2700 2500 3000 PDI by GPC 1.2 1.2 1.2

TABLE 3a In-situ preparation of zirconium metal-ligand compositions andsolution premix and injection details. Example # 4.1 4.2 4.3 4.4 4.5Metal Precursor Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(NMe₂)₄Ligand Ligand D Ligand C Ligand E Ligand G Ligand C Metal PrecursorSolution 0.010 0.010 0.010 0.010 0.010 Concentration (M) Metal PrecursorVolume (mL) 0.040 0.040 0.040 0.040 0.040 μmol of metal added to 1 mLvial 0.40 0.40 0.40 0.40 0.40 Ligand Solution concentration (M) 0.0250.025 0.025 0.025 0.025 Ligand Solution Volume (mL) 0.032 0.032 0.0320.032 0.032 μmol of Ligand added to 1 mL vial 0.080 0.080 0.080 0.0800.080 Complexation Time 1 hour 1 hour 1 hour 1 hour 1.5 hoursComplexation Temperature 70° C. 70° C. 70° C. 70° C. 80° C. Solventvolume lost to evaporation 0.030 0.030 0.030 0.030 0.080 Volume ofSolvent Added to vial 0 0 0.100 0.100 0.070 (mL) Initial Solvent Volume(mL) 0.050 0.050 0.150 0.150 0.070 Volume of 0.5 M 1-octene solution0.024 0.024 0.024 0.024 0.024 added to vial (mL) Premix Alkyl (group 13reagent) MMAO MMAO MMAO PMAO-IP DIBAL-H Premix Alkyl concentration (M)0.050 0.050 0.050 0.050 0.20 Premix Alkyl Volume (mL) 0.048 0.048 0.0480.048 0.060 Premix Alkyl/Zr ratio 6/1 6/1 6/1 6/1 30/1 Activator (2.5mM) ABF20 ABF20 ABF20 ABF20 ABF20 Activator Volume (mL) 0.176 0.1760.176 0.176 0.176 Activator/Zr ratio 1.1/1 1.1/1 1.1/1 1.1/1 1.1/1Injection Fraction 0.050 0.050 0.025 0.025 0.25 Injection Volume (mL)0.015 0.015 0.010 0.010 0.083 μmol Zr injected into reactor 0.020 0.0200.010 0.010 0.10

TABLE 3b Results of ethylene-styrene copolymerizations employingzirconium metal-ligand compositions. Example # 4.1 4.2 4.3 4.4 4.5 MetalPrecursor Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(CH₂Ph)₄ Zr(NMe₂)₄ LigandLigand D Ligand C Ligand E Ligand G Ligand C μmol Zr injected intoreactor 0.020 0.020 0.010 0.010 0.10 Run Time (Minutes) 15.0 3.6 2.3 1.53.1 Polymer Yield (mg) 105 128 211 141 108 Activity (mg polymer per 3481801 9183 9200 347 μmol Zr per minute) mol percent incorporated 10.310.1 — — — Styrene by ¹H NMR mol percent total styrene by 12.1 12.8 8.26.6 13.7 FTIR (linear regression) Mw by GPC 3200 2400 3600 2600 Mw/Mn byGPC 1.2 1.2 1.3 1.2

TABLE 4a In-situ preparation of hafnium metal-ligand compositions andsolution premix and injection details. Example # 4.6 4.7 4.8 4.9 4.10Metal Precursor Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(NMe₂)₄Ligand Ligand D Ligand C Ligand E Ligand G Ligand C Metal PrecursorSolution 0.010 0.010 0.010 0.010 0.010 concentration (M) Metal PrecursorVolume (mL) 0.040 0.040 0.040 0.040 0.040 μmol of metal added to 1 mLvial 0.40 0.40 0.40 0.40 0.40 Ligand Solution concentration 0.025 0.0250.025 0.025 0.025 (M) Ligand Solution Volume (mL) 0.032 0.032 0.0320.032 0.032 μmol of Ligand added to 1 mL 0.080 0.080 0.080 0.080 0.080vial Complexation Time 1 hour 1 hour 1 hour 1 hour 1.5 hoursComplexation Temperature 70° C. 70° C. 70° C. 70° C. 80° C. Solventvolume lost to 0.030 0.030 0.030 0.030 0.080 evaporation Volume ofSolvent Added to vial 0 0 0 0 0.070 (mL) Initial Solvent Volume (mL)0.050 0.050 0.050 0.050 0.070 Volume of 0.5 M 1-octene 0.024 0.024 0.0240.024 0.024 solution added to vial (mL) Premix Alkyl (group 13 reagent)MMAO MMAO MMAO PMAO-IP DIBAL-H Premix Alkyl concentration (M) 0.0500.050 0.050 0.050 0.20 Premix Alkyl Volume (mL) 0.048 0.048 0.048 0.0480.060 Premix Alkyl/Zr ratio 6/1 6/1 6/1 6/1 30/1 Activator (2.5 mM)ABF20 ABF20 ABF20 ABF20 ABF20 Activator Volume (mL) 0.176 0.176 0.1760.176 0.176 Activator/Zr ratio 1.1/1 1.1/1 1.1/1 1.1/1 1.1/1 InjectionFraction 0.25 0.25 0.25 0.05 0.50 Injection Volume (mL) 0.075 0.0750.075 0.015 0.165 μmol Zr injected into reactor 0.10 0.10 0.10 0.0200.20

TABLE 4b Results of ethylene-styrene copolymerizations employing hafniummetal-ligand compositions. Example # 4.6 4.7 4.8 4.9 4.10 MetalPrecursor Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(CH₂Ph)₄ Hf(NMe₂)₄ LigandLigand D Ligand C Ligand E Ligand G Ligand C μmol Hf injected intoreactor 0.10 0.10 0.10 0.020 0.20 Run Time (Minutes) 15.0 15.0 3.8 15 15Polymer Yield (mg) 61 84 194 70 97 Activity (mg polymer per μmol 41 56506 230 32 Hf per minute) mol percent total styrene by 8.2 5.0 2.6 3.45.6 FTIR (linear regression) Mw by GPC 6800 3200 8000 5500 Mw/Mn by GPC1.5 1.2 1.6 1.4

As described above, embodiments of the invention provide a number ofuseful articles of manufacture, including but not limited to, waxes,lubricants, additives, processing aids, etc. The waxes may be used toformulate paints and coatings, printing inks, carbon paper, phototoners, building and construction materials, mold release agents, hotmelt adhesives, candles. The waxes may also be used in wood processing,metal working, powder metallurgy and sintering, wax modeling, sizing,crop protection, and so on.

While the invention has been described with respect to a limited numberof embodiments, these embodiments are not intended to limit the scope ofthe invention as otherwise described and claimed herein. Variations andmodifications therefrom exist. The appended claims intend to cover allsuch variations and modifications as falling within the scope of theinvention.

1. An article of manufacture, comprising: a linear copolymer of ethyleneand vinyl aromatic monomer having a weight average molecular weight ofless than 15,000, wherein the copolymer is characterized by a backbonehaving a first and second terminal end group, the first terminal endgroup is a methyl group, the second terminal end group is a vinyl group,wherein the ratio of the terminal methyl group to the terminal vinylgroup is 0.8:1 to 1:0.8.
 2. The article of manufacture of claim 1,wherein the backbone of the copolymer is substantially free of avinylidene group.
 3. The article of manufacture of claim 1, wherein thearticle is a wax.
 4. The article of manufacture of claim 1, wherein thearticle is a hot melt adhesive.
 5. The article of manufacture of claim1, wherein the article is an electrostatic toner.
 6. The article ofmanufacture of claim 1, wherein the article is a lubricant.
 7. Thearticle of manufacture of claim 1, wherein the copolymer includes afunctional group.
 8. The article of manufacture of claim 7, wherein thefunctional group is a halogen, hydroxyl, anhydride, amine, amide,carboxylic acid, ester, ether, or nitrile group.
 9. A method offunctionalizing a polymer, comprising: obtaining a linear copolymer ofethylene and vinyl aromatic monomer having a weight average molecularweight of less than 15,000, the copolymer being characterized by abackbone having a first and second terminal end group, the firstterminal end group being a methyl group, the second terminal end groupbeing a vinyl group, wherein the ratio of the terminal methyl group tothe terminal vinyl group is 0.8:1 to 1:0.8; and effectuatingfunctionalization of the vinyl group to make a functionalized copolymer.10. The method of claim 9, wherein the functionalization ischlorination.
 11. The method of claim 9, wherein the functionalizationis epoxidation.
 12. The method of claim 9, wherein the functionalizationis oxidation.
 13. The method of claim 9, wherein the functionalizationis carboxylation.
 14. The method of claim 9, wherein thefunctionalization is sulfonation.